CN104693134A - S-triazine derivate monomer and preparing method for polyarylether fluorescent material - Google Patents
S-triazine derivate monomer and preparing method for polyarylether fluorescent material Download PDFInfo
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- CN104693134A CN104693134A CN201510133998.7A CN201510133998A CN104693134A CN 104693134 A CN104693134 A CN 104693134A CN 201510133998 A CN201510133998 A CN 201510133998A CN 104693134 A CN104693134 A CN 104693134A
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- fluorescent material
- polyarylether
- triazine
- fluorophenyl
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 229920000090 poly(aryl ether) Polymers 0.000 title claims abstract description 34
- 239000000178 monomer Substances 0.000 title claims abstract description 30
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title abstract description 14
- AEKVBBNGWBBYLL-UHFFFAOYSA-N 4-fluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1 AEKVBBNGWBBYLL-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 p-fluorobenzonitrile compound Chemical class 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 16
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- NUHWHLSPHBVPKM-UHFFFAOYSA-N 2,4,6-tris(4-fluorophenyl)-1,3,5-triazine Chemical compound C1=CC(F)=CC=C1C1=NC(C=2C=CC(F)=CC=2)=NC(C=2C=CC(F)=CC=2)=N1 NUHWHLSPHBVPKM-UHFFFAOYSA-N 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- QXAITBQSYVNQDR-ZIOPAAQOSA-N amitraz Chemical compound C=1C=C(C)C=C(C)C=1/N=C/N(C)\C=N\C1=CC=C(C)C=C1C QXAITBQSYVNQDR-ZIOPAAQOSA-N 0.000 claims description 3
- 229960002587 amitraz Drugs 0.000 claims description 3
- UDYFLDICVHJSOY-UHFFFAOYSA-N sulfur trioxide pyridine complex Chemical group O=S(=O)=O.C1=CC=NC=C1 UDYFLDICVHJSOY-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- DXASQZJWWGZNSF-UHFFFAOYSA-N n,n-dimethylmethanamine;sulfur trioxide Chemical compound CN(C)C.O=S(=O)=O DXASQZJWWGZNSF-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 238000011175 product filtration Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 229930185605 Bisphenol Natural products 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract 1
- 230000003628 erosive effect Effects 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- WRLZCIKDGHGUAT-UHFFFAOYSA-N 3-(4-hydroxyphenyl)-1H-pyridazin-6-one Chemical group C1=CC(O)=CC=C1C1=NNC(=O)C=C1 WRLZCIKDGHGUAT-UHFFFAOYSA-N 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- WETHGUDKVUSVNL-UHFFFAOYSA-N Fc(cc1)ccc1C1=NSOC(c(cc2)ccc2F)=N1 Chemical compound Fc(cc1)ccc1C1=NSOC(c(cc2)ccc2F)=N1 WETHGUDKVUSVNL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- YKYMGFHOJJOSEB-UHFFFAOYSA-N butan-1-ol;potassium Chemical compound [K].CCCCO YKYMGFHOJJOSEB-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
Abstract
The invention relates to an S-triazine derivate monomer and a preparing method for a polyarylether fluorescent material and belongs to the technical field of organic synthesis, macromolecule synthesis, fluorescent materials and light converting. According to the technical scheme, p-fluorobenzonitrile is adopted as a starting raw material, p-fluorobenzonitrile and a p-fluorobenzonitrile compound are synthesized into a 2,4,6-tri(4-fluorophenyl)-1,3,5-S-triazine monomer through a two-step method, and the S-triazine monomer and one or more bisphenol monomers are prepared into a polyarylether fluorescent material through a one-step method. The S-triazine derivate monomer has the advantages that the monomer synthesis yield is high, purity is high, reaction time is short, energy consumption is low, and the cost is saved; the prepared polyarylether fluorescent material has the advantages that the yield is high, the fluorescence intensity is high, the thermal stability is high, and the material resists chemical erosion.
Description
Technical field
The invention belongs to organic synthesis, Polymer Synthesizing, fluorescent material, turn light technical field, particularly relate to the preparation method of a kind of s-triazine derivative monomer and polyarylether fluorescent material.
Background technology
Poly-(triaryl-1,3,5-s-triazine) there is unique s-triazine ring and aromatic ring planar conjugate structure, make it to show excellent over-all properties, as thermostability, photoelectric property, resistance to chemical attack, high strength, high-moduluss etc., thus have broad application prospects in the field such as fire-retardant, photoelectricity, sorbing material.Wherein, build poly-(triaryl-1,3,5-s-triazine), because of the stereoeffect of its uniqueness and conjugated structure, can be applicable to the field such as sorbing material and photoelectric material.The synthesis of build poly-(triaryl-1,3,5-s-triazine) is generally realize by being reacted by addition, replacement etc. containing the reactive monomer of triaryl s-triazine structure and other reactive monomers.It is important polymerization approach that 2,4,6-tri-(4-halogenophenyl)-1,3,5-triazines and Polyphenols or halogenated monomer react.
2,4,6-tri-(4-fluorophenyl)-1,3,5-triazine is as important polymerization single polymerization monomer, and its synthetic method is rare report in document at home and abroad, take p-Fluorophenyl cyanide as starting raw material synthesis 2,4, the report of 6-tri-(4-fluorophenyl)-1,3,5-triazines, only has single stage method at present.This method makes catalyzer with zinc chloride, obtained at 270 DEG C of reaction 64h by p-Fluorophenyl cyanide, productive rate is 40% (Ricarda Berger, J ü rg Hauser, et al.New symmetrically substituted 1,3,5-triazinesas host compounds for channel-type inclusion formation.CrystEngComm, 2014,14:768-770.).Although this method synthesis step is simple, temperature of reaction is high, long reaction time, and energy consumption is high, and productive rate is on the low side, and cost is higher.
Containing triaryl-1,3, the polyarylether compounds of 5-s-triazine structure has good thermostability, photoelectric property, the advantages such as resistance to chemical attack, but it is few to the research report of this respect, its application is mainly limited by 2,4,6-tri-(4-fluorophenyl)-1, the complicated preparation process of 3,5-triazine monomers and lower productive rate.
Summary of the invention
The object of the invention is to, overcome the deficiencies in the prior art, provide a kind of high yield, high purity, less energy-consumption, low cost synthesis 2,4,6-tri-(4-fluorophenyl)-1, the method of 3,5-triazine monomers, and provide a kind of method preparing high yield, fluorescent both, superior heat-stability polyarylether class fluorescent material.
Feature of the present invention is that monomer synthesize yield is high, and purity is high, and the reaction times is short, and energy consumption is low, cost-saving.The preparation characteristic of polyarylether class fluorescent material is that yield is high, and fluorescence intensity is high, Heat stability is good, resistance to chemical attack etc.
For solving the problems of the technologies described above, technical scheme of the present invention is: take p-Fluorophenyl cyanide as starting raw material, with to fluorobenzene formamidine compound through two step synthesis 2,4,6-tri-(4-fluorophenyl)-1,3,5-triazine monomers, s-triazine monomer prepares polyarylether class fluorescent material through single stage method and one or more class biphenol monomers.The molecular structural formula of 2,4,6-tri-(4-fluorophenyl)-1,3,5-triazines that the present invention relates to and the general formula of polyarylether class fluorescent material are respectively:
Wherein, A represents structural unit:
in one or more;
B represents structural unit:
A preparation method for s-triazine derivative, specifically comprises two steps:
(1) p-Fluorophenyl cyanide is dissolved in Nitromethane 99Min., adds sulfur trioxide complex, obtained cyclic intermediate 4,6-bis-(4-fluorophenyl)-2-oxo 1,2,3,5-oxa-thiodiazine; Reaction formula is as follows:
(2) intermediate and to fluorobenzene formamidine compound in molar ratio for 1:(1-3) be dissolved in aprotic polar solvent, under organic base catalytic, stir 0-3h in 0-50 DEG C, be 50-150 DEG C in temperature and heat 0-3h, be cooled to room temperature, add solvent, be settled out product and suction filtration, washing, dry, obtained 2,4,6-tri-(4-fluorophenyl)-1,3,5-triazine, reaction formula is as follows:
In step of the present invention (1), first p-Fluorophenyl cyanide is dissolved in nitromethane solution, adds sulfur trioxide complex, reaction generation 4,6-bis-(4-fluorophenyl)-2-oxo 1,2,3,5-oxa-thiodiazine intermediate.This is a thermopositive reaction, and high temperature easily causes raw material generation sulfonation reaction.Therefore, reaction should be controlled at 0-50 DEG C; Reaction times 0-3h.Then, suction filtration, washing, dry, obtain intermediate.Recyclable raw material p-Fluorophenyl cyanide and ether, alcoholic solvent in wash filtrate.
In step of the present invention (2), by intermediate with aprotic polar solvent is dissolved in fluorobenzene formamidine compound, add organic bases, make reaction system be alkaline environment, be conducive to the acidic substance produced in neutralization reaction, be beneficial to reaction forward and carry out.Stir 0-3h at 0-50 DEG C, then at 50-150 DEG C of backflow 0-3h, make reaction more abundant, improve productive rate.Cool to room temperature, suction filtration, alcohols washs, without the need to recrystallization, Liquid Detection purity 100%.
In step of the present invention (1), the quality consumption of p-Fluorophenyl cyanide is 0.2-3 times of Nitromethane 99Min.; Be to fluorobenzene carbonamidine or to fluorobenzene amitraz hydrochloride to fluorobenzene formamidine compound in step (1).In step (1), sulfur trioxide complex is sulfur trioxide-pyridine mixture, sulfur trioxide-trimethylamine mixture, sulphur trioxide-DMF complex compound or sulphur trioxide, and its mole dosage is 1-3 times of p-Fluorophenyl cyanide.
In step of the present invention (2), aprotic polar solvent is acetone, DMF or tetrahydrofuran (THF), and its quality consumption is 1-5 times of solute; Solvent in step (2) is water, methyl alcohol or acetonitrile, and its quality consumption is 1-5 times of Nitromethane 99Min..In step (2), organic bases is sodium methylate, potassium ethylate or potassium tert.-butoxide, and its mole dosage is 1-5 times of reactant.
The polyarylether class fluorescent material prepared by s-triazine derivative, general structure is as follows:
Wherein
A represents structural unit:
in one or more;
B represents structural unit:
The preparation method of described polyarylether class fluorescent material, concrete steps are: by 2,4,6-tri-(4-fluorophenyl)-1,3,5-triazines and class biphenol monomer 2:(1-5 in molar ratio) be dissolved in solvent and water entrainer, add catalyzer, be the 100-160 DEG C of 1-5h that dewaters in temperature, at 150-220 DEG C, react 1-12h, pour in the water containing hydrochloric acid and alcohol, suction filtration, grinds, and uses the soxhlet extraction removal of impurity, vacuum-drying, obtained polyarylether class fluorescent material.Reaction formula is as follows:
Solvent described in the preparation method of above-mentioned polyarylether class fluorescent material is the one or several arbitrarily in N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or tetramethylene sulfone, and its quality consumption is 5-20 times of reactant.2,4,6-tri-(4-fluorophenyl)-1,3,5-triazines monomer and class biphenol monomer are dissolved in solvent and water entrainer, and solvent for use has good solubility to reactant, has good compatibility to reaction system, are conducive to the molecular weight improving polymkeric substance.
Described water entrainer is chlorobenzene, toluene or dimethylbenzene, and its volumetric usage is 1-10 times of solvent.Add water entrainer, be conducive to promoting that reaction forward is carried out.
Described catalyzer is sodium carbonate, salt of wormwood or sodium bicarbonate, and its mole dosage is 1-3 times of reactant.
Body is basic nucleophilic substitution reaction, and alkali, in the reaction as catalyzer, captures class biphenol monomer and three halogenated monomers react the H generated
+and F
-, be conducive to accelerating speed of reaction and improving level of response.
The invention has the beneficial effects as follows: 2,4,6-tri-(the 4-fluorophenyls)-1 that the present invention describes, the two-step approach of 3,5-triazine synthesis take p-Fluorophenyl cyanide as starting raw material, 4,6-bis-(4-fluorophenyl)-2-oxo 1,2 is catalyzed and synthesized through sulfur trioxide complex, 3,5-oxa-thiodiazine, then with fluorobenzene formamidine compound is reacted to obtained, reaction characteristics is that yield is high, and purity is high, and the reaction times is short, energy consumption is low, cost-saving.Single stage method prepared by the polyarylether fluorescent material described in invention is with 2,4,6-tri-(4-fluorophenyl)-1,3,5-triazine and class biphenol monomer carry out nucleophilic substitution reaction and obtain, and the feature of such material is that yield is high, fluorescence is strong, Heat stability is good, resistance to chemical attack.The present inventor not yet finds to disclose in existing technology two-step approach of the present invention and prepares the method that 2,4,6-tri-(4-fluorophenyl)-1,3,5-triazines and single stage method prepare polyarylether fluorescent material.
Below in conjunction with specific embodiment, the present invention will be further described.
Accompanying drawing explanation
Fig. 1 is 2,4,6-tri-(4-fluorophenyl)-1,3,5-triazines monomer
1h NMR spectrogram.The display of this spectrogram only has two groups of peaks, and to go out peak position consistent with the proton hydrogen kind in this s-triazine monomer and nucleus magnetic hydrogen spectrum theory, describes the synthesized high purity of s-triazine monomer and the exactness of chemical structure.
Fig. 2 is the solid of the polyarylether fluorescent material containing 6-(4-hydroxy phenyl) pyridazine-3 (2H)-one structure
13c NMR spectrogram.The peak that the proton carbon can telling different positions by this spectrogram produces, goes out peak position with the carbon spectral theory in this materials chemistry structure and matches, demonstrate the exactness of material structure.
Fig. 3 is the fluorescence spectrum figure of the polyarylether fluorescent material containing 6-(4-hydroxy phenyl) pyridazine-3 (2H)-one structure.This fluorogram illustrates the distribution situation of material Emission spectrum, can determine that this material has fluorescence, and the light launched is blue light.
Fig. 4 is the hot weightless picture of polyarylether fluorescent material under nitrogen and air atmosphere containing 6-(4-hydroxy phenyl) pyridazine-3 (2H)-one structure.In figure, display material just starts to occur obvious weightlessness being warming up to about 400 DEG C, indicates this material and has good thermostability and thermo-oxidative stability.
Embodiment
For better understanding technical scheme of the present invention, be described in further detail by following specific embodiment.
Raw material explanation
6-(4-hydroxy phenyl) pyridazine-3 (2H)-one used in embodiment, phthalazone reference J.Xu, Y.Z.Meng, S.J.Wang, A.S.Hay.Journal of Polymer Science Part A:PolymerChemistry.2006,44, method described in 10 is synthesized.
Embodiment 1
Be dissolved in 20mL Nitromethane 99Min. by p-Fluorophenyl cyanide (12.11g, 0.1mol) under room temperature, ice-water bath is cooled to 10 DEG C, add sulfur trioxide-pyridine mixture (23.87g, 0.15mol), at room temperature stir 1h, add anhydrous diethyl ether, suction filtration, ether and washing with alcohol are for several times, vacuum-drying, obtained 4,6-bis-(4-fluorophenyl)-2-oxo 1,2,3,5-oxa-thiodiazine, yield is 75%.Fusing point: 132.2-133.9 DEG C.FTIR (KBr): 1680cm
-1(C=N stretching vibration peak), 1586cm
-1, 1530cm
-1, 1477cm
-1(stretching vibration that phenyl ring skeleton produces), 1215cm
-1(S=O stretching vibration), 851cm
-1(C-H flexural vibration peak).
By 4,6-bis-(4-fluorophenyl)-2-oxo 1,2,3,5-oxa-thiodiazine (3.22g, 0.01mol) with to fluorobenzene amitraz hydrochloride (1.75g, 0.01mol) be dissolved in 50mL acetone, add propyl carbinol potassium (3.37,0.03mol), stirring at normal temperature 1h, is heated to 50 DEG C and reacts 1h.Cool to room temperature, adds deionized water, suction filtration, methanol wash, dry 3.09g 2,4,6-tri-(4-fluorophenyl)-1,3,5-triazines, yield 85%, purity 100% (high performance liquid phase test).Fusing point: 261.6-262.5 DEG C.FTIR (KBr): 1602cm
-1, 1523cm
-1, 1507cm
-1(stretching vibration that phenyl ring skeleton produces), 859cm
-1, 861cm
-1(C-H flexural vibration peak).Anal.calcd for C
21h
12n
3f
3: C 69.42, H 3.33, N 11.57; Found:C 68.90, H3.36, N 11.46. (Elemental analysis data of monomer)
1h NMR (400MHz, CDCl
3): δ 8.86 – 8.69 (m, 1H), 7.40 – 7.17 (m, 1H), as shown in Figure 1.
Embodiment 2
Is being furnished with water trap, reflux condensing tube, by 2 in the 100mL round-bottomed flask of mechanical stirring and nitrogen conduit, 4,6-tri-(4-fluorophenyl)-1,3,5-triazines (1.82g, 0.005mol) with 6-(4-hydroxy phenyl) pyridazine-3 (2H)-one (1.41g, 0.0075mol) be dissolved in 20mL N,N-dimethylacetamide, add toluene 50mL, add salt of wormwood (1.38g, 0.01mol), be warming up to 150 DEG C of 2h that dewater, remove toluene and water, be warming up to 170 DEG C of reactions to not stirring, and be incubated 1h.Product is poured in the aqueous solution containing hydrochloric acid and methyl alcohol, suction filtration, and methyl alcohol and water washing are dry.Ball mill grinds, and surname extraction is except desolventizing and unreacting material, and vacuum-drying, obtains 3.04g polyarylether s-triazine product.Productive rate is 94%.FTIR:3446cm
-1(O-H, N-H stretching vibration peak), 1679cm
-1(C=O, C=N stretching vibration peak), 1596cm
-1, 1540cm
-1, 1499cm
-1(stretching vibration that phenyl ring skeleton produces), 1239cm
-1(C-O-C stretching vibration peak), 874cm
-1, 819cm
-1(C-H flexural vibration peak), as shown in Figure 2.
Embodiment gained polyarylether fluorescent material is distributed in deionized water, excites with 370nm excitation wavelength, measure the fluorescence intensity at its emission wavelength 400-600nm place, as shown in Figure 3.
By embodiment gained polyarylether fluorescent material with the temperature rise rate of 20 DEG C/min, carry out thermogravimetric test in 50-800 DEG C.Thermogravimetric spectrogram under nitrogen and air atmosphere, as shown in Figure 4.
Embodiment 3
Is being furnished with water trap, reflux condensing tube, by 2 in the 100mL round-bottomed flask of mechanical stirring and nitrogen conduit, 4,6-tri-(4-fluorophenyl)-1,3,5-triazines (1.82g, 0.005mol) with '-biphenyl diphenol (1.49g, 0.008mol) be dissolved in 25mL N,N-dimethylacetamide, add toluene 60mL, add salt of wormwood (1.38g, 0.01mol), be warming up to 150 DEG C of 2h that dewater, remove toluene and water, be warming up to 170 DEG C of reactions to not stirring, and be incubated 1h.Product is poured in the aqueous solution containing hydrochloric acid and methyl alcohol, suction filtration, and methyl alcohol and water washing are dry.Ball mill grinds, and surname extraction is except desolventizing and unreacting material, and vacuum-drying, obtains 2.93g polyarylether s-triazine product.Productive rate is 91%.FTIR:3390cm
-1(O-H, N-H stretching vibration peak), 1600cm
-1, 1550cm
-1, 1490cm
-1(stretching vibration that phenyl ring skeleton produces), 1239cm
-1(C-O-C stretching vibration peak), 874cm
-1, 819cm
-1(C-H flexural vibration peak).Solid-state
13c NMR (400MHz, H
2sO
4-d
2, ppm): 178.7,170.5,165.2,159.6,143.9,128.6,119.4,78.3,29.8.
Embodiment gained polyarylether fluorescent material is carried out fluorometric investigation, and under maximum excitation wavelength 390nm condition, record its emission wavelength within the scope of 420-640nm, maximum emission wavelength is 490nm.
Thermogravimetric analysis is tested, and under air atmosphere, temperature of initial decomposition is 340 DEG C, and carbon yield is 5%; Under nitrogen atmosphere, temperature of initial decomposition is 370 DEG C, and carbon yield is 21%.
Embodiment 4
Is being furnished with water trap, reflux condensing tube, by 2 in the 100mL round-bottomed flask of mechanical stirring and nitrogen conduit, 4,6-tri-(4-fluorophenyl)-1,3,5-triazines (1.82g, 0.005mol) with phthalazone (1.79g, 0.0075mol) be dissolved in 25mL N,N-dimethylacetamide, add toluene 60mL, add salt of wormwood (1.38g, 0.01mol), be warming up to 150 DEG C of 2h that dewater, remove toluene and water, be warming up to 170 DEG C of reactions to not stirring, and be incubated 1h.Product is poured in the aqueous solution containing hydrochloric acid and methyl alcohol, suction filtration, and methyl alcohol and water washing are dry.Ball mill grinds, and surname extraction is except desolventizing and unreacting material, and vacuum-drying, obtains 3.15g polyarylether s-triazine product.Productive rate is 87%.Productive rate is 94%.FTIR:3460cm
-1(O-H, N-H stretching vibration peak), 1685cm
-1(C=O, C=N stretching vibration peak), 1590cm
-1, 1530cm
-1, 1496cm
-1(stretching vibration that phenyl ring skeleton produces), 1245cm
-1(C-O-C stretching vibration peak), 890cm
-1, 826cm
-1(C-H flexural vibration peak), solid-state
13c NMR (400MHz, H
2sO
4-d
2, ppm): 219.5,206.2,181.4,172.4,166.1,163.4,156.7,147.2,135.9,119.7,82.3,45.2.
Be distributed in deionized water by embodiment gained polyarylether fluorescent material, excite with 370nm excitation wavelength, record its emission wavelength within the scope of 410-600nm, maximum emission wavelength is 450nm.
By embodiment gained polyarylether fluorescent material with the temperature rise rate of 20 DEG C/min, carry out thermogravimetric test in 50-800 DEG C.Under recording air atmosphere, temperature of initial decomposition is 320 DEG C, and carbon yield is 0%; Under nitrogen atmosphere, temperature of initial decomposition is 350 DEG C, and carbon yield is 17%.
Claims (10)
1. a preparation method for s-triazine derivative, is characterized in that, specifically comprises two steps:
(1) p-Fluorophenyl cyanide is dissolved in Nitromethane 99Min., adds sulfur trioxide complex, obtained cyclic intermediate 4,6-bis-(4-fluorophenyl)-2-oxo 1,2,3,5-oxa-thiodiazine; Reaction formula is as follows:
(2) intermediate and to fluorobenzene formamidine compound in molar ratio for 1:(1-3) be dissolved in aprotic polar solvent, under organic base catalytic, stir 0-3h in 0-50 DEG C, be 50-150 DEG C in temperature and heat 0-3h, be cooled to room temperature, add solvent, be settled out product and suction filtration, washing, dry, obtained 2,4,6-tri-(4-fluorophenyl)-1,3,5-triazine, reaction formula is as follows:
2. the preparation method of s-triazine derivative according to claim 1, is characterized in that, in described step (1) the quality consumption of p-Fluorophenyl cyanide be the 0.2-3 of Nitromethane 99Min. doubly; In step (1), sulfur trioxide complex is sulfur trioxide-pyridine mixture, sulfur trioxide-trimethylamine mixture, sulphur trioxide-DMF complex compound or sulphur trioxide, and its mole dosage is 1-3 times of p-Fluorophenyl cyanide.
3. the preparation method of s-triazine derivative according to claim 1, is characterized in that, is to fluorobenzene carbonamidine or to fluorobenzene amitraz hydrochloride to fluorobenzene formamidine compound in described step (2).
4. the preparation method of s-triazine derivative according to claim 1, is characterized in that, in described step (2), aprotic polar solvent is acetone, DMF or tetrahydrofuran (THF), its quality consumption be the 1-5 of solute doubly; Solvent in step (2) is water, methyl alcohol or acetonitrile, and its quality consumption is 1-5 times of Nitromethane 99Min..
5. the preparation method of s-triazine derivative according to claim 1, is characterized in that, in described step (2), organic bases is sodium methylate, potassium ethylate or potassium tert.-butoxide, its mole dosage be the 1-5 of reactant doubly.
6. the polyarylether class fluorescent material prepared by s-triazine derivative, it is characterized in that, general structure is as follows:
Wherein
A represents structural unit:
in one or more;
B represents structural unit:
7. the preparation method of polyarylether class fluorescent material according to claim 6, is characterized in that: concrete steps are:
By 2,4,6-tri-(4-fluorophenyl)-1,3,5-triazine and class biphenol monomer 2:(1-5 in molar ratio) be dissolved in solvent and water entrainer, add catalyzer, be the 100-160 DEG C of 1-5h that dewaters in temperature, at 150-220 DEG C, react 1-12h, pour in the water containing hydrochloric acid and alcohol, suction filtration, grind, use the soxhlet extraction removal of impurity, vacuum-drying, obtained polyarylether class fluorescent material.
8. the preparation method of polyarylether class fluorescent material according to claim 7, it is characterized in that, described solvent is the one or several arbitrarily in N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or tetramethylene sulfone, and its quality consumption is 5-20 times of reactant.
9. the preparation method of polyarylether class fluorescent material according to claim 7, it is characterized in that, described water entrainer is chlorobenzene, toluene or dimethylbenzene, its volumetric usage be the 1-10 of solvent doubly.
10. the preparation method of polyarylether class fluorescent material according to claim 7, it is characterized in that, described catalyzer is sodium carbonate, salt of wormwood or sodium bicarbonate, its mole dosage be the 1-3 of reactant doubly.
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| CN115612435A (en) * | 2022-10-20 | 2023-01-17 | 唯万科技有限公司 | High-temperature-resistant polyurethane adhesive for sealing and preparation method thereof |
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| CN115612435A (en) * | 2022-10-20 | 2023-01-17 | 唯万科技有限公司 | High-temperature-resistant polyurethane adhesive for sealing and preparation method thereof |
| CN115612435B (en) * | 2022-10-20 | 2023-09-12 | 唯万科技有限公司 | High-temperature-resistant polyurethane adhesive for sealing and preparation method thereof |
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