CN112940014B - Thiophene derivative and synthesis method and application thereof - Google Patents
Thiophene derivative and synthesis method and application thereof Download PDFInfo
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- CN112940014B CN112940014B CN202110147274.3A CN202110147274A CN112940014B CN 112940014 B CN112940014 B CN 112940014B CN 202110147274 A CN202110147274 A CN 202110147274A CN 112940014 B CN112940014 B CN 112940014B
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- 150000003577 thiophenes Chemical class 0.000 title claims abstract description 27
- 238000001308 synthesis method Methods 0.000 title description 2
- 239000000839 emulsion Substances 0.000 claims abstract description 30
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000005033 polyvinylidene chloride Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 87
- 239000000243 solution Substances 0.000 claims description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 28
- 239000012074 organic phase Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000003480 eluent Substances 0.000 claims description 23
- 239000000741 silica gel Substances 0.000 claims description 23
- 229910002027 silica gel Inorganic materials 0.000 claims description 23
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 claims description 22
- 229910000080 stannane Inorganic materials 0.000 claims description 22
- 238000004440 column chromatography Methods 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- 238000011282 treatment Methods 0.000 claims description 11
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- -1 (2, 3-dihydrothieno [3,4-B ] [1,4] dioxin) -9,9' -spirobifluorene Chemical compound 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- BKPKAXNQLXUGJP-UHFFFAOYSA-N O=C(CO1)OC2C1=CSC2 Chemical compound O=C(CO1)OC2C1=CSC2 BKPKAXNQLXUGJP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 7
- 230000003712 anti-aging effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- UPJLZKCEPFAKSH-UHFFFAOYSA-N 2',7'-dibromo-9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC(Br)=CC=C1C1=CC=C(Br)C=C12 UPJLZKCEPFAKSH-UHFFFAOYSA-N 0.000 claims description 5
- MZIBVRNBPBPEKJ-UHFFFAOYSA-N CCCCC1OC2=CSC=C2OC1(CCCC)CCCC Chemical compound CCCCC1OC2=CSC=C2OC1(CCCC)CCCC MZIBVRNBPBPEKJ-UHFFFAOYSA-N 0.000 claims description 5
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 claims description 4
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 6
- 238000001914 filtration Methods 0.000 claims 1
- 230000000996 additive effect Effects 0.000 abstract description 6
- 238000004383 yellowing Methods 0.000 abstract description 5
- 238000010189 synthetic method Methods 0.000 abstract description 4
- VPVXHAANQNHFSF-UHFFFAOYSA-N 1,4-dioxan-2-one Chemical compound O=C1COCCO1 VPVXHAANQNHFSF-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 14
- 239000004800 polyvinyl chloride Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000012047 saturated solution Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005452 food preservative Substances 0.000 description 1
- 235000019249 food preservative Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/08—Homopolymers or copolymers of vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a thiophene derivative (E2SBFE2) shown as a formula 1, 2, 7-di (2,2 ', 3,3 ' -tetrahydro-5, 5 ' -dithio-thieno [3, 4-b)][1,4]Dioxanone) -9,9' -spirobifluorene, a synthetic method thereof and application thereof as a polymer emulsion additive; the E2SBFE2 can be used as an additive to be compounded with PVDC emulsion to prepare composite emulsion E2SBFE2@ PVDC, the composite emulsion is particularly suitable for being coated on PVC and other hard sheets to prepare composite hard sheets, and the composite emulsion has the advantage of strong anti-yellowing capability;
Description
Technical Field
The invention relates to a novel thiophene derivative 2, 7-bis (2,2 ', 3, 3' -tetrahydro-5, 5 '-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene, a synthetic method thereof and application thereof as a polymer emulsion additive.
Background
Polyvinylidene chloride (PVDC) has a head-to-tail linear polymer chain structure, chlorine atoms in molecules of the PVDC have hydrophobicity, cannot form hydrogen bonds, can effectively block water vapor and oxygen, is a packaging material with better comprehensive blocking performance at present, and is widely applied to the packaging fields of food preservative films, medicine packaging materials and the like. However, both PVDC emulsion and PVDC emulsion coated composite materials have the problem of yellowing and aging easily under long-term sunlight irradiation, so that research on suitable additives is needed to further improve the performance of the PVDC emulsion and the PVDC composite materials.
Disclosure of Invention
The invention provides a new thiophene derivative molecule 2, 7-di (2,2 ', 3, 3' -tetrahydro-5, 5 '-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene (E2SBFE2 for short), a synthetic method thereof and application thereof as a polymer emulsion (particularly PVDC) additive.
In order to achieve the purpose, the invention adopts the following technical scheme:
a thiophene derivative (E2SBFE2) shown in formula 1,
the invention also provides a synthetic method of the thiophene derivative shown in the formula 1, which comprises the following steps:
(1) adding 3, 4-ethylenedioxythiophene (EDOT for short) into dry dichloromethane in a nitrogen atmosphere, dropwise adding n-hexane solution of n-butyllithium at 0 ℃, continuously stirring for 0.5-5 h (preferably 1h), dropwise adding tributyltin chloride, continuously stirring for 0.5-3 h (preferably 1h), transferring to the normal temperature, continuously stirring for 6-60 h (preferably 12h), and carrying out aftertreatment on the obtained reaction liquid A to obtain tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxanone) stannane A (EDOT-Sn for short); the mass ratio of the 3, 4-ethylenedioxythiophene to the n-butyllithium to the tributyltin chloride is 1: 0.5-6.0: 0.2 to 20 (preferably 1: 1.05: 1.1);
(2) adding 2, 7-dibromo-9, 9 '-spirobifluorene (Br-SBF-Br for short), bis (triphenylphosphine) palladium dichloride and tributyl (2, 3-dihydrothieno [3,4-B ] [1,4] dioxin) stannane B in the step (1) into toluene A under a nitrogen atmosphere, heating and refluxing for 10-100 h (preferably 24h), cooling to room temperature, and carrying out post-treatment on the obtained reaction liquid B to obtain 2, 7-bis (2, 3-dihydrothieno [3,4-B ] [1,4] dioxin) -9,9' -spirobifluorene (EDOT-SBF-EDOT for short); the ratio of the amounts of the 2, 7-dibromo-9, 9' -spirobifluorene, bis (triphenylphosphine) palladium dichloride and tributyl (2, 3-dihydrothieno [3,4-B ] [1,4] dioxane) stannane B species was 1: 0.01-0.1: 0.5 to 5.0 (preferably 1: 0.03: 2.2);
(3) adding the 2, 7-bis (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) -9,9 '-spirobifluorene and N-bromosuccinimide into tetrahydrofuran in a dark environment, continuously stirring for 4-80 h (preferably 24h) at room temperature, and carrying out aftertreatment on the reaction liquid C to obtain 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene (Br-EDOT-SBF-EDOT-Br for short); the mass ratio of the 2, 7-bis (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene to the N-bromosuccinimide is 1: 0.2-10 (preferably 1: 2.2);
(4) adding the 2, 7-bis (7-bromo-2, 3-dithieno [3,4-B ] [1,4] dioxin) -9,9' -spirobifluorene and bis triphenylphosphine palladium dichloride in the step (3) and tributyl (2, 3-dihydrothieno [3,4-B ] [1,4] dioxin) stannane C in the step (1) into toluene B under a nitrogen atmosphere, heating and refluxing for 10-60 h (preferably 24h), cooling to room temperature, and carrying out aftertreatment on the obtained reaction liquid D to obtain a thiophene derivative (2, 7-bis (2,2 ', 3,3 ' -tetrahydro-5, 5 ' -dithieno [3,4-B ] [1,4] dioxin) -9,9' -spirobifluorene, short for E2SBFE2) shown in the formula 1; the mass ratio of 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene, bis triphenylphosphine palladium dichloride and tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxane) stannane C was 1: 0.01-0.1: 0.5 to 5.0 (preferably 1: 0.03: 2.2).
Toluene a and toluene B are both toluene and are distinguished herein by toluene a and toluene B for convenience of description and without any other special meaning. Tributyl (2, 3-dihydrothieno [3,4-B ] [1,4] dioxane) stannane A, tributyl (2, 3-dihydrothieno [3,4-B ] [1,4] dioxane) stannane B, tributyl (2, 3-dihydrothieno [3,4-B ] [1,4] dioxane) stannane C are also for convenience of description and have no other special meaning.
Further, the volume of the dried dichloromethane in the step (1) is 20-30ml/g, preferably 25ml/g based on the mass of the 3, 4-Ethylenedioxythiophene (EDOT).
Further, the concentration of n-butyllithium in the n-hexane solution of n-butyllithium in the step (1) is 1.2 to 6.0mol/L, preferably 2.4 mol/L.
Further, the volume of toluene A in step (2) is 40 to 50ml/g, preferably 45ml/g, based on the tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxane) stannane.
Further, the volume of tetrahydrofuran in the step (3) is 20 to 40ml/g, preferably 30ml/g based on the mass of 2, 7-bis (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene.
Further, the volume of toluene B in the step (4) is 80 to 100ml/g, preferably 90ml/g based on the mass of 2, 7-bis (7-bromo-2, 3-dithieno [3,4-B ] [1,4] dioxin) -9,9' -spirobifluorene.
Further, the post-treatment step A in the step (1) is as follows: adding dichloromethane with the volume equal to that of the reaction solution A and a saturated sodium chloride solution with the volume equal to that of the reaction solution A into the reaction solution A, extracting for 3 times, combining organic phases, adding anhydrous sodium sulfate, stirring (30 minutes), drying, performing suction filtration to remove the sodium sulfate, adding silica gel powder into the dried organic phase, removing the organic solution by using a rotary evaporator, mixing samples, performing separation and purification on the obtained crude product by using a chromatographic column chromatography method and taking dichloromethane as an eluent, detecting by TLC, collecting the eluent containing a target product, and performing rotary evaporation to remove the solvent to obtain the tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxanone) stannane; the adsorption phase of the chromatographic column chromatography is 100-200 mesh aluminum oxide.
The post-treatment B in the step (2) comprises the following steps: adding dichloromethane and saturated sodium chloride solution which are equal in volume to the reaction solution B into the reaction solution B, extracting for 3 times, combining organic phases, adding anhydrous sodium sulfate, stirring (30 minutes), drying, performing suction filtration to remove the sodium sulfate, adding silica gel powder into the dried organic phase, removing the organic solution by using a rotary evaporator, stirring, separating and purifying the obtained crude product by using chromatographic column chromatography by using a mixed solution of dichloromethane and petroleum ether with a volume ratio of 1:3 as an eluent, detecting by TLC, collecting the eluent containing the target product, and performing rotary evaporation to remove the solvent to obtain the 2, 7-bis (2, 3-dihydrothieno [3,4-B ] [1,4] dioxanone) -9,9' -spirobifluorene stannane; the adsorption phase of the chromatographic column chromatography is 300-400 mesh silica gel.
The post-treatment C in the step (3) comprises the following steps: adding dichloromethane with the volume equal to that of the reaction solution C and saturated sodium chloride solution with the volume equal to that of the reaction solution A into the reaction solution C, extracting for 3 times, combining organic phases, adding anhydrous sodium sulfate, stirring (30 minutes), drying, performing suction filtration to remove the sodium sulfate, adding silica gel powder into the dried organic phase, removing the organic solution by using a rotary evaporator, mixing samples, separating and purifying the obtained crude product by using a chromatographic column chromatography method and a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:4 as eluent, detecting by TLC, collecting the eluent containing the target product, and performing rotary evaporation to remove the solvent to obtain the 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxanone) -9,9' -spirobifluorene; the adsorption phase of the chromatographic column chromatography is 300-400 mesh silica gel.
The post-treatment D in the step (4) comprises the following steps: adding dichloromethane with the volume equal to that of the reaction solution D and a saturated sodium chloride solution with the volume equal to that of the reaction solution A into the reaction solution D, extracting for 3 times, combining organic phases, adding anhydrous sodium sulfate, stirring (30 minutes), drying, performing suction filtration to remove the sodium sulfate, adding silica gel powder into the dried organic phase, removing the organic solution by using a rotary evaporator, mixing the sample, separating and purifying the obtained crude product by using a chromatographic column chromatography method and using a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:2 as an eluent, detecting by TLC, collecting the eluent containing the target product, and performing rotary evaporation to remove the solvent to obtain the thiophene derivative shown in the formula 1; wherein the adsorption phase of the chromatographic column chromatography is 300-400 mesh silica gel.
In the above post-treatments A to D, the amount of silica gel powder added is preferably such that the product is completely adsorbed, the effect is to stabilize the product and to improve the yield and purity, and the subsequent steps of spin-drying, chromatography and the like can be performed without mixing the silica gel powder, but the yield is reduced.
The invention provides application of a thiophene derivative shown in the formula 1 as an additive of a polymer anti-aging emulsion.
Further, the application is as follows: adding a thiophene derivative (E2SBFE2) shown in a formula 1 into the aqueous emulsion of the polymer, fully stirring, and uniformly mixing to obtain a composite emulsion; the mass ratio of the thiophene derivative represented by the formula 1 to the aqueous emulsion of the polymer is 1: 1000-50000 (preferably 1: 20000).
Preferably, the polymer anti-aging emulsion is a PVDC aqueous emulsion, and the composite emulsion is E2SBFE2@ PVDC.
The PVDC emulsion is prepared according to the method of the embodiment 1 of Chinese patent publication No. CN 104114585A.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a novel thiophene derivative E2SBFE2 and a preparation method thereof, wherein E2SBFE2 can be used as an additive to be compounded with PVDC emulsion to prepare composite emulsion E2SBFE2@ PVDC, and the composite emulsion is particularly suitable for being coated on hard sheets such as PVC (polyvinyl chloride) and the like to prepare composite hard sheets and has the advantage of strong anti-yellowing capability.
Drawings
Fig. 1 is a synthetic route of the novel thiophene derivative E2SBFE 2: : the synthetic route of the E2SBFE2 is shown as the following, wherein 1 is EDOT-Sn, 2 is EDOT-SBF-EDOT, 3 is Br-EDOT-SBF-EDOT-Br, and 4 is a final product E2SBFE 2;
FIG. 2 is a comparison of UV-visible light transmittance curves of the PVC/E2SBFE2@ PVDC composite hard sheet prepared in example 1 and the PVC/PVDC composite hard sheet.
FIG. 3 is a nuclear magnetic hydrogen spectrum of E2SBFE 2.
FIG. 4 is a mass spectrum of E2SBFE 2.
FIG. 5 is the color change curve of the PVC/E2SBFE2@ PVDC and PVC/PVDC composite hard sheet after xenon lamp irradiation test
Detailed Description
Example 1
The preparation process of the novel thiophene derivative E2SBFE2 comprises the following steps:
(1) adding 20g of 3, 4-ethylenedioxythiophene into 500 ml of ultra-dry dichloromethane under the nitrogen atmosphere, placing the mixture in an environment at 0 ℃, dropwise adding 70 ml of 2.4mol/L n-butyllithium n-hexane solution into the obtained solution, continuously stirring the solution for 1 hour, then dropwise adding 50 g of tributyltin chloride into the solution, further stirring the solution for 1 hour, taking the solution out of the environment at 0 ℃, placing the solution at normal temperature, and continuously stirring the solution for 12 hours. Adding 600mL of dichloromethane and 600mL of sodium chloride saturated solution into 600mL of solution obtained after the reaction is finished, extracting for 3 times, combining the obtained organic phases, adding 20g of anhydrous sodium sulfate into the solution, stirring for 30 minutes, drying, performing suction filtration after the completion of the reaction to remove the sodium sulfate, adding 40g of silica gel powder into the dried organic phase, removing the organic solution by using a rotary evaporator, separating and purifying the obtained crude product by chromatographic column chromatography, wherein the adsorption phase is 100-200-mesh aluminum oxide, the eluent is dichloromethane, performing TLC identification, collecting the eluent containing the target product, and removing the solvent by rotary evaporation to obtain 45g of tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxanone) stannane.
(2) Adding 10g of 2, 7-dibromo-9, 9' -spirobifluorene, 442 mg of bistriphenylphosphine palladium dichloride and 20g of tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxane) stannane prepared in (1) into 900mL of toluene under a nitrogen atmosphere, heating and refluxing for 24 hours, cooling to room temperature, adding 900mL of dichloromethane and 900mL of a sodium chloride saturated solution into 900mL of the solution obtained after the reaction is finished, extracting for 3 times, combining the obtained organic phases, adding 20g of anhydrous sodium sulfate thereto, stirring for 30 minutes, drying, performing suction filtration after completion, removing the sodium sulfate therefrom, adding 10g of silica gel powder into the dried organic phase and removing the organic solution by using a rotary evaporator, and separating and purifying the obtained crude product by chromatography, wherein the adsorption phase is 300-mesh 400-mesh silica gel, the eluent is dichloromethane and petroleum ether is 1:3(v/v), TLC identification is carried out, eluent containing the target product is collected, and the solvent is removed through rotary evaporation to obtain 12g of the product 2, 7-bis (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene.
(3) Adding 10g of 2, 7-bis (2, 3-dihydrothieno [3,4-b ] [1,4] dioxanone) -9,9' -spirobifluorene and 6.7 g of N-bromosuccinimide into 300mL of tetrahydrofuran in a dark environment, standing the mixture at room temperature, stirring the mixture for 24 hours, adding 300mL of dichloromethane and 300mL of saturated sodium chloride solution into the 300mL of solution after the reaction is finished, extracting the mixture for 3 times, combining the obtained organic phases, adding 20g of anhydrous sodium sulfate into the combined organic phases, stirring the combined organic phases for 30 minutes, drying the mixture, performing suction filtration after the reaction is finished, removing the sodium sulfate from the combined organic phases, adding 10g of silica gel powder into the dried organic phases, removing the organic solution by using a rotary evaporator, separating and purifying the obtained crude product by a chromatographic column chromatography, wherein the adsorption phase is 300-400-mesh silica gel, the dichloromethane is petroleum ether which is 1:4(v/v), TLC identification, collecting the eluent containing the target product, and removing the solvent by rotary evaporation to obtain 11g of the product 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxanone) -9,9' -spirobifluorene.
(4) 10g of 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene obtained in (3) and 12g of tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxane) stannane prepared in (1) were added to 900mL of toluene under nitrogen atmosphere and heated under reflux for 24 hours, after cooling to room temperature, 900mL of methylene chloride and 900mL of a saturated solution of sodium chloride were added to 900mL of the reaction liquid obtained after the completion of the reaction, the obtained organic phases were combined, 20g of anhydrous sodium sulfate was added thereto and stirred for 30 minutes to dry, suction filtration was performed after completion, the sodium sulfate therein was removed, 8g of a silica gel powder was added to the dried organic phase and the organic solution was removed by means of a rotary evaporator, the obtained crude product is separated and purified by chromatographic column chromatography, wherein the adsorption phase is 300-400 mesh silica gel, the eluent is dichloromethane and petroleum ether which are 1:2(v/v), TLC identification is carried out, the eluent containing the target product is collected, and the solvent is removed by rotary evaporation, so that 7.2g of the product E2SBFE2 is obtained, and the nuclear magnetic spectrum and the mass spectrum of the product are shown in figures 3 and 4.
Preparation of PVC/E2SBFE2@ PVDC composite hard sheet:
carrying out corona discharge treatment on the surface of a PVC hard sheet (the thick bottom is 250 microns), coating a layer of polyurethane adhesive of 2 g/square meter on the surface, drying for 15 seconds at 80 ℃ in a hot air circulation dryer, coating E2SBFE2@ PVDC composite emulsion prepared by 60 g/square meter on the surface, drying for 20 seconds at 80 ℃ in the hot air circulation dryer, and then placing in a drying room for curing for 48 hours at 50 ℃, thus finishing the preparation of the PVC/E2SBFE2@ PVDC composite hard sheet.
Placing PVC/E2SBFE2@ PVDC composite hard sheet at the ultraviolet light intensity of 3000uW/cm2The aging degree of the composite hard sheet was observed under different time periods, and the results are shown in Table 2.
Comparative example
PVDC emulsion was prepared according to the procedure of example 1.
The preparation method comprises the steps of carrying out corona discharge treatment on the surface of a PVC hard sheet (the thick bottom is 250 microns), coating a layer of polyurethane adhesive of 2 g/square meter on the surface, drying for 15 seconds at 80 ℃ in a hot air circulation dryer, coating PVDC emulsion prepared by 60 g/square meter on the surface, drying for 20 seconds at 80 ℃ in the hot air circulation dryer, and then placing the PVC hard sheet in a drying room for curing for 48 hours at 50 ℃ to finish the preparation of the PVC/PVDC composite hard sheet.
According to the national standard GB/T16422.1-2019 plastic laboratory light source exposure test method, the ultraviolet radiation resistance (anti-aging yellowing performance) of the PVC/E2SBFE2@ PVDC and the ultraviolet radiation resistance (anti-aging yellowing performance) of the PVC/PVDC composite hard sheet in the comparative example are compared, and the test result is shown in FIG. 5.
Claims (8)
1. A thiophene derivative shown as a formula 1,
2. a method for synthesizing the thiophene derivative represented by formula 1 according to claim 1, comprising the steps of:
(1) adding 3, 4-ethylenedioxythiophene into dry dichloromethane in a nitrogen atmosphere, dropwise adding n-hexane solution of n-butyl lithium at 0 ℃, continuously stirring for 0.5-5 h, dropwise adding tributyltin chloride, continuously stirring for 0.5-3 h, transferring to normal temperature, continuously stirring for 6-60 h, and carrying out aftertreatment treatment on the obtained reaction liquid A to obtain tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxanone) stannane; the mass ratio of the 3, 4-ethylenedioxythiophene to the n-butyllithium to the tributyltin chloride is 1: 0.5-6.0: 0.2 to 20;
(2) adding 2, 7-dibromo-9, 9 '-spirobifluorene, bis (triphenylphosphine) palladium dichloride and tributyl (2, 3-dihydrothieno [3,4-B ] [1,4] dioxin) stannane in the step (1) into toluene in a nitrogen atmosphere, heating and refluxing for 10-100 h, cooling to room temperature, and carrying out aftertreatment on the obtained reaction liquid B to obtain 2, 7-bis (2, 3-dihydrothieno [3,4-B ] [1,4] dioxin) -9,9' -spirobifluorene; the ratio of the amounts of the 2, 7-dibromo-9, 9' -spirobifluorene, bis (triphenylphosphine) palladium dichloride and tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxane) stannane species was 1: 0.01-0.1: 0.5 to 5.0;
(3) adding the 2, 7-bis (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) -9,9 '-spirobifluorene and N-bromosuccinimide into tetrahydrofuran in a dark environment, continuously stirring for 4-80 h at room temperature, and carrying out aftertreatment on the obtained reaction liquid C to obtain 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene; the mass ratio of the 2, 7-bis (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene to the N-bromosuccinimide is 1: 0.2-10;
(4) adding the 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene and bis triphenylphosphine palladium dichloride in the step (3) and tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) stannane in the step (1) into toluene under a nitrogen atmosphere, heating and refluxing for 10-60 h, cooling to room temperature, and carrying out aftertreatment on the obtained reaction liquid D to obtain a thiophene derivative shown in the formula 1; the mass ratio of 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene, bis triphenylphosphine palladium dichloride and tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) stannane was 1: 0.01-0.1: 0.5 to 5.0.
3. The method for synthesizing a thiophene derivative represented by formula 1 according to claim 2, wherein: the volume of the dried dichloromethane in the step (1) is 20-30ml/g based on the mass of the 3, 4-ethylenedioxythiophene; the volume of toluene in step (2) is 40-50ml/g based on the tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxane) stannane; the volume of the tetrahydrofuran in the step (3) is 20-40ml/g based on the mass of the 2, 7-bis (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene; the volume of toluene in step (4) is 80 to 100ml/g based on the mass of 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxin) -9,9' -spirobifluorene.
4. The method for synthesizing a thiophene derivative represented by formula 1 according to claim 2, wherein: the post-treatment step A in the step (1) comprises the following steps: adding dichloromethane with the volume equal to that of the reaction solution A and a saturated sodium chloride solution with the volume equal to that of the reaction solution A into the reaction solution A, extracting for 3 times, combining organic phases, adding anhydrous sodium sulfate, stirring and drying, performing suction filtration to remove the sodium sulfate, adding silica gel powder into the dried organic phase, removing the organic solution by using a rotary evaporator, mixing samples, performing separation and purification on the obtained crude product by using a chromatographic column chromatography method and taking dichloromethane as an eluent, detecting by TLC, collecting the eluent containing a target product, and performing rotary evaporation to remove a solvent to obtain the tributyl (2, 3-dihydrothieno [3,4-b ] [1,4] dioxanone) stannane; the adsorption phase of the chromatographic column chromatography is 100-200 mesh aluminum oxide.
5. The method for synthesizing a thiophene derivative represented by formula 1 according to claim 2, wherein: the post-treatment B in the step (2) comprises the following steps: adding dichloromethane with the volume equal to that of the reaction liquid B and saturated sodium chloride solution with the volume equal to that of the reaction liquid A into the reaction liquid B, extracting for 3 times, combining organic phases, adding anhydrous sodium sulfate, stirring and drying, performing suction filtration to remove sodium sulfate, adding silica gel powder into the dried organic phase, removing the organic solution by using a rotary evaporator, stirring, separating and purifying the obtained crude product by using chromatographic column chromatography and a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:3 as an eluent, detecting by TLC, collecting the eluent containing a target product, and removing the solvent by rotary evaporation to obtain the 2, 7-bis (2, 3-dihydrothieno [3,4-B ] [1,4] dioxanone) -9,9' -spirobifluorene stannane; the adsorption phase of the chromatographic column chromatography is 300-400 mesh silica gel.
6. The method for synthesizing a thiophene derivative represented by formula 1 according to claim 2, wherein: the post-treatment C in the step (3) comprises the following steps: adding dichloromethane with the volume equal to that of the reaction solution C and a saturated sodium chloride solution with the volume equal to that of the reaction solution A into the reaction solution C, extracting for 3 times, combining organic phases, adding anhydrous sodium sulfate, stirring and drying, filtering to remove sodium sulfate, adding silica gel powder into the dried organic phase, removing the organic solution by using a rotary evaporator, stirring, separating and purifying the obtained crude product by using a chromatographic column chromatography method and using a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:4 as an eluent, detecting by TLC, collecting the eluent containing the target product, and removing the solvent by rotary evaporation to obtain the 2, 7-bis (7-bromo-2, 3-dithieno [3,4-b ] [1,4] dioxane) -9,9' -spirobifluorene; the adsorption phase of the chromatographic column chromatography is 300-400 mesh silica gel.
7. The method for synthesizing a thiophene derivative represented by formula 1 according to claim 2, wherein: the post-treatment D in the step (4) comprises the following steps: adding dichloromethane with the volume equal to that of the reaction solution D and a saturated sodium chloride solution with the volume equal to that of the reaction solution A into the reaction solution D, extracting for 3 times, combining organic phases, adding anhydrous sodium sulfate, stirring and drying, performing suction filtration to remove sodium sulfate, adding silica gel powder into the dried organic phase, removing the organic solution by using a rotary evaporator, mixing the sample, separating and purifying the obtained crude product by using chromatographic column chromatography with a mixed solution of dichloromethane and petroleum ether with the volume ratio of 1:2 as an eluent, detecting by TLC, collecting the eluent containing the target product, and performing rotary evaporation to remove the solvent to obtain the thiophene derivative shown in the formula 1; wherein the adsorption phase of the chromatographic column chromatography is 300-400 mesh silica gel.
8. The use of thiophene derivatives according to claim 1 as additives for polymeric anti-aging emulsions, characterized in that said use is: adding the thiophene derivative shown in the formula 1 into the aqueous emulsion of the polymer, fully stirring, and uniformly mixing to obtain a composite emulsion; the mass ratio of the thiophene derivative shown in the formula 1 to the aqueous emulsion of the polymer is 1: 1000-50000; the polymer anti-aging emulsion is PVDC aqueous emulsion.
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| CN108948599A (en) * | 2018-08-02 | 2018-12-07 | 洛阳兴瑞新材料科技有限公司 | A kind of color inhibition modified polyvinilidene polyvinylidene chloride resin and preparation method |
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| CN108485399A (en) * | 2018-03-02 | 2018-09-04 | 浙江衢州巨塑化工有限公司 | A kind of coating PVDC water-based emulsions |
| CN108948599A (en) * | 2018-08-02 | 2018-12-07 | 洛阳兴瑞新材料科技有限公司 | A kind of color inhibition modified polyvinilidene polyvinylidene chloride resin and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| Production of Nanostructured Conjugated Polymers by Electropolymerization of Tailored Tetrahedral Precursors;Ali Yassin et al.;《Chem.Electro.Chem.》;20140527;第1卷(第7期);第1219-1225页 * |
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