CN106749403A - A kind of flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide and preparation method thereof - Google Patents
A kind of flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide and preparation method thereof Download PDFInfo
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- CN106749403A CN106749403A CN201611123983.3A CN201611123983A CN106749403A CN 106749403 A CN106749403 A CN 106749403A CN 201611123983 A CN201611123983 A CN 201611123983A CN 106749403 A CN106749403 A CN 106749403A
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- Prior art keywords
- flame
- quinoline
- retardant
- difluorophenyl
- phosphine oxide
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 59
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 33
- HMHNFCPNFVFXKN-UHFFFAOYSA-N [PH3]=O.FC1=C(C(=NC2=CC=CC=C12)C1=CC=CC=C1)F Chemical compound [PH3]=O.FC1=C(C(=NC2=CC=CC=C12)C1=CC=CC=C1)F HMHNFCPNFVFXKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 difluorophenyl flame-retardant Chemical compound 0.000 claims abstract description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- RYGIHSLRMNXWCN-UHFFFAOYSA-N quinoline-3-carbaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CN=C21 RYGIHSLRMNXWCN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000005282 brightening Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920006351 engineering plastic Polymers 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000012209 synthetic fiber Substances 0.000 claims description 4
- 229920002994 synthetic fiber Polymers 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- PHGRKTBHLLCFND-UHFFFAOYSA-N CC1=CC=C(C=C1)[PH2]=O Chemical class CC1=CC=C(C=C1)[PH2]=O PHGRKTBHLLCFND-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 abstract description 2
- QBMYSSONSQDJPR-UHFFFAOYSA-N P.FC1=C(C(=NC2=CC=CC=C12)C1=CC=CC=C1)F Chemical compound P.FC1=C(C(=NC2=CC=CC=C12)C1=CC=CC=C1)F QBMYSSONSQDJPR-UHFFFAOYSA-N 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- DEOXRZRSVLAHSG-UHFFFAOYSA-N 3,4-difluoro-2-phenylquinoline Chemical compound FC1=C(C(=NC2=CC=CC=C12)C1=CC=CC=C1)F DEOXRZRSVLAHSG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 229940121710 HMGCoA reductase inhibitor Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004079 fireproofing Methods 0.000 description 2
- 239000002471 hydroxymethylglutaryl coenzyme A reductase inhibitor Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KUSYBTQDVDCOPO-UHFFFAOYSA-N C1CC1C2=C3C(=CC=C2)N=C(C(=C3F)F)C4=CC=CC=C4 Chemical compound C1CC1C2=C3C(=CC=C2)N=C(C(=C3F)F)C4=CC=CC=C4 KUSYBTQDVDCOPO-UHFFFAOYSA-N 0.000 description 1
- KDYJCWRYYAUJDN-UHFFFAOYSA-N FC(C1=CC=CC=C1N=C1C2=CC=CC=C2)=C1F.[O] Chemical compound FC(C1=CC=CC=C1N=C1C2=CC=CC=C2)=C1F.[O] KDYJCWRYYAUJDN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 239000003524 antilipemic agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004212 difluorophenyl group Chemical group 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- VGYFMXBACGZSIL-MCBHFWOFSA-N pitavastatin Chemical compound OC(=O)C[C@H](O)C[C@H](O)\C=C\C1=C(C2CC2)N=C2C=CC=CC2=C1C1=CC=C(F)C=C1 VGYFMXBACGZSIL-MCBHFWOFSA-N 0.000 description 1
- 229960002797 pitavastatin Drugs 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/60—Quinoline or hydrogenated quinoline ring systems
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- 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
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- 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
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
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- 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
- C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Fireproofing Substances (AREA)
Abstract
The invention discloses difluorophenyl flame-retardant luminous bifunctional material of quinoline phosphine oxide shown in a kind of Formulas I and preparation method thereof, the present invention is combined by by two kinds of functional structure cell rings PrFs for phenylchinoline and phosphine oxide group, form a kind of new with flame-retardant luminous difunctional difluorophenyl quinoline phosphine oxide-type compound, increased the new varieties of fire retardant and ultra-violet light-emitting material.Preparation method of the present invention, process is simple, safety and environmental protection, it is suitable to industrialized production, the prepared flame-retardant luminous bifunctional material dissolubility of difluorophenyl quinoline phosphine oxide is good, heat endurance and chemical stability are high, and processability is good, has fire-retardant and luminous dual-use function concurrently, fluorine, phosphorus and nitrogen multielement synergy can be realized, preferable flame-retarded efficiency is shown, excellent UV-light emission characteristics can be showed again, be widely used.
Description
Technical field：
The present invention relates to fire proofing and technical field of organic luminescence materials, and in particular to a kind of difluorophenyl quinoline oxidation
Flame-retardant luminous bifunctional material of phosphine and preparation method thereof.
Background technology：
Fire retardant is widely used in electronic apparatus, communication, nuclear power, Aero-Space, traffic, building materials, interior decoration, weaving etc.
Field, is one of important measures of scientific prevention and cure fire.With the development and the progress of science and technology of society, the application field of fire retardant
Constantly expand, requirement of the countries in the world to each zone material and fire block articles performance be further strict, to the research and development of fire retardant with should
New requirement is it is also proposed with technology.Therefore, the research and development of new and effective, multifunction fire retardant are current fire proofing research and development
One of important topic, with extremely important realistic meaning.
Cyclopropyl difluorophenyl quinoline is a kind of important pharmacophoric group, is that statins antilipemic drugs of new generation cut down him
The effective efficiency construction unit in spit of fland.2- cyclopropyl -4- (4- difluorophenyls) quinoline-3-formaldehyde is the weight of medicine Pitavastatin synthesis
Intermediate is wanted, it is studied be limited to synthetic method, technical study more in the prior art, and as medicine intermediate in synthesis
Cut down the application in statins.Recently, we are public respectively in Chinese patent ZL201310219327.3 and CN103555319A
A kind of difluorophenyl quinoline glyoxaline compound and fluorine-containing ring the third quinoline schiff base compounds are opened, this two classes compound has
There is blue-light-emitting characteristic, can be used for the fields such as luminescent device, sensitive fluorescent.However, the research of this kind of compound is extremely limited, plant
Class is also less, is not directed to research of this kind of compound as novel flame redundant material.Particularly, by functional structure unit fluorobenzene
, through simple, effectively combination, formation has the difluorophenyl quinoline oxygen of fire-retardant and luminous dual-use function concurrently for base quinoline and phosphine oxide group
Change phosphine compound, there is not been reported in the prior art.
The content of the invention：
It is an object of the invention to provide a kind of flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide.
The present invention is achieved by the following technical programs：
A kind of difluorophenyl flame-retardant luminous bifunctional material of quinoline phosphine oxide shown in Formulas I：
The synthetic route of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide of the invention is as follows：
The preparation method of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide of the invention, comprises the following steps：
It is 1 by mol ratio:0.8~1.2 2- cyclopropyl -4- (4- difluorophenyls) quinoline-3-formaldehyde (compound ii) and
Double (p-methylphenyl) phosphine oxides (compound III) are dissolved in organic solvent, are stirred at reflux reaction 4~6 hours, and rotary evaporation is removed
Solvent is removed, through recrystallization, vacuum drying, target product is obtained.
The organic solvent is toluene or dioxane or toluene-methanol；Described recrystallization be using methyl alcohol or methyl alcohol-
Toluene, or methyl alcohol-tetrahydrofuran carries out recrystallization operation for solvent.
The flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide of the invention is white solid powder, and its fusing point is
209.66 DEG C (DSC peak values), the compound is 50% in 255 DEG C of weightlessness, and at 800 DEG C, carbon yield is 4.51%.The compound
With preferable dissolubility, heat endurance and flame-retarding characteristic, can not only be used for reactive type fire retardant for epoxy resin, polyester,
The flame retarded polymeric materials such as polyamide, can also be used among engineering plastics as additive flame retardant.
The present invention also protects the application of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide, used as reactivity
Type fire retardant is used for epoxy resin, polyester, polyamide flame retarded polymeric material or is used for engineering plastics as additive flame retardant
Among；Or, being used for luminescent device, anti-fake material, fluorescent brightening, fluorescence sense field as ultra-violet light-emitting material；Or, as hair
Light type fire retardant is used for fire-fighting, traffic, electronic apparatus, cable, plastics and synthetic fibers field.
The flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide of the invention has UV-light luminous special in solid-state
Property, launch wavelength is 360nm, can be used for luminescent device, anti-fake material, fluorescent brightening, sensitive fluorescent as ultra-violet light-emitting material
Deng field.
The flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide of the invention can be used to disappear as light emitting-type fire retardant
The fields such as anti-, traffic, electronic apparatus, cable, plastics and synthetic fibers.
The present invention has the advantages that：
(1) present invention is combined by by two kinds of functional structure cell rings PrFs for phenylchinoline and phosphine oxide group,
Form a kind of new with flame-retardant luminous difunctional difluorophenyl quinoline phosphine oxide-type compound, increased fire retardant and purple
The new varieties of outer luminescent material.
(2) in the molecular structure of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide of the invention containing fluorine, phosphorus,
Three kinds of ignition-proof elements of nitrogen, can give full play to fluoro- phosphorus-nitrogen cooperative flame retardant synergistic effect, so as to realize ternary with different fire retardant mechanisms
Synergistic, fluoro- phosphorus-nitrogen cooperative flame retardant efficiency is high, overcomes the deficiency of single ignition-proof element.
(3) multiple benzene are contained in the molecular structure of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide of the invention
Ring structure and C-P, C-F key, these design features are conducive to improving the heat endurance and chemical stability of compound, can be adapted to many
Plant the high temperature process of macromolecular material.The introducing of fluorine atom in molecule, largely changes the physical chemistry of compound
Matter so that its application performance is improved by a relatively large margin, can strengthen the chemical stability of molecule, can carry high molecular compatible again
Property.The presence of strong C-F keys, changes molecular energy level structure, aggregated structure or packing of molecules form, so as to cause organic light
The change of electric material processability, and the concentration quenching of luminescent material can be effectively reduced, improve luminous efficiency so as to reach
Purpose.The presence of cyclopropyl, can be effectively increased the steric hindrance of molecule, suppress the crystallization of material, reduce crystallinity, so that
Compound has good filming performance, compatibility, increases the processability of material；Meanwhile, concentration quenching can be also reduced, promote
Enter luminous efficiency raising.Additionally, the introducing of cyclopropyl can also increase the solubility of this kind of compound.
(4) removed in the flame-retardant luminous bifunctional material molecular structure of difluorophenyl quinoline phosphine oxide of the invention and contain fluorobenzene
Outside two kinds of functional groups of base quinoline and phosphine oxide, also contain hydroxyl, therefore, also can be as reactive flame retardant, by above-mentioned resistance
Combustion construction unit is incorporated into the molecular structure of macromolecular material, so as to while Material Physics mechanical performance is not influenceed, carry
The fire resistance and durability of macromolecular material high.
(5) the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide of the present invention has good purple in the case of solid-state
Outer smooth emission characteristics, its fluorescence emission peak is 360nm.The luminescent material is in fluorescent brightening, anti-fake material, sensitive fluorescent, luminous
The fields such as device have potential using value.
(6) new way of the organic material of fire-retardant and luminous dual-use function is had concurrently the invention provides a kind of quick acquisition,
The research field of difluorophenyl quinolines is expanded.
(7) preparation method of the invention, process is simple is easy to operate, without inert gas shielding, it is easy to control, easily
Purifying, equipment investment is few, and the equal recoverable of organic solvent used, safety and environmental protection is suitable to industrialized production.Simultaneously as institute
Raw material is selected to be the intermediate of the industries such as medicine, therefore, and comprehensive development and utilization for related industry, industrial upgrading provide one
The new effective way of bar.
In a word, preparation method of the present invention, process is simple, safety and environmental protection are suitable to industrialized production, prepared difluorophenyl
The flame-retardant luminous bifunctional material dissolubility of quinoline phosphine oxide is good, heat endurance and chemical stability are high, and processability is good, has concurrently
Fire-retardant and luminous dual-use function, can realize fluorine, phosphorus and nitrogen multielement synergy, show preferable flame-retarded efficiency, again may be used
Excellent UV-light emission characteristics is showed, is widely used, epoxy resin can be used for as reactive type fire retardant, gathered
Ester, polyamide flame retarded polymeric material are used among engineering plastics as additive flame retardant；Or, as ultra-violet light-emitting material
For luminescent device, anti-fake material, fluorescent brightening, sensitive fluorescent field；Or, as light emitting-type fire retardant be used for fire-fighting, traffic,
Electronic apparatus, cable, plastics and synthetic fibers field.As reactive type fire retardant or as additive flame retardant.
Brief description of the drawings：
Fig. 1 is the infrared spectrogram of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide of the invention；
Fig. 2 is the hot weightless picture of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide of the invention；
Fig. 3 is the solid state fluorescence spectrogram of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide of the invention.
Specific embodiment：
Further illustrated the following is to of the invention, rather than limitation of the present invention.
Laboratory apparatus and model：Bruker AVANCE-300 nuclear magnetic resonance chemical analysers；Nicolet Magna 760 are infrared
Spectrometer；TA DSC Q20 differential scanning calorimeters；The thermogravimetric analyzers of Netzsch TG 209；HORIBA Jobin Yvon
Aqualog absorbs and three-dimensional fluorescence scanning spectrometer.
Embodiment 1：The preparation of the flame-retardant luminous bifunctional material (compound I) of difluorophenyl quinoline phosphine oxide
By 2- cyclopropyl -4- (4- difluorophenyls) quinoline-3-formaldehyde (compound ii, 0.10mol) and double (to methylbenzene
Base) phosphine oxide (compound III, 0.10mol) is dissolved in 100 milliliters of toluene, is stirred at reflux reaction 4-6 hour, rotary evaporation removing
Solvent, separates out white solid, and crude product recrystallizing methanol, vacuum drying obtains target product, and yield is 73%.DSC is measured
Fusing point is 209.66 DEG C (peak value).
1H NMR(300MHz,DMSO-d6/TMS)δ:0.19(m,1H),0.79(m,1H),0.95(m,1H),1.06(m,
1H), 2.30 (s, 3H), 2.36 (s, 3H), 2.81 (m, 1H), 5.70-5.76 (m, 1H), 6.72-6.81 (m, 1H), 6.99-
7.07 (m, 2H), 7.14-7.40 (m, 10H), 7.59-7.66 (m, 3H), 7.81 (d, J=8.4Hz, 1H).IR(KBr)ν:
3061,2921,2865,1602,1569,1556,1512,1490,1411,1225,1159,1115,1095,1075,1047,
1020,900,842,806,764,718,653,549cm-1.Its infrared spectrogram is as shown in Figure 1.
The thermal weight loss performance of compound is tested with the thermogravimetric analyzers of Netzsch TG 209, Fig. 2 is seen.From Figure 2 it can be seen that should
Compound is 50% in 255 DEG C of weightlessness, and at 800 DEG C, carbon yield is 4.51%, with preferable heat endurance and flame-retarding characteristic.
Embodiment 2：The preparation of the flame-retardant luminous bifunctional material (compound I) of difluorophenyl quinoline phosphine oxide
By 2- cyclopropyl -4- (4- difluorophenyls) quinoline-3-formaldehyde (compound ii, 0.10mol) and double (to methylbenzene
Base) phosphine oxide (compound III, 0.12mol) is dissolved in 100 milliliters of dioxane, is stirred at reflux reaction 4-6 hours, rotary evaporation
Solvent is removed, white solid is separated out, crude product is recrystallized with methanol-toluene, vacuum drying obtains target product, and yield is
71%.
Embodiment 3：The preparation of the flame-retardant luminous bifunctional material (compound I) of difluorophenyl quinoline phosphine oxide
By 2- cyclopropyl -4- (4- difluorophenyls) quinoline-3-formaldehyde (compound ii, 0.10mol) and double (to methylbenzene
Base) phosphine oxide (compound III, 0.08mol) is dissolved in 100 milliliters of toluene-methanols (volume ratio is 3:1) in, it is stirred at reflux reaction 4-
6 hours, rotary evaporation removed solvent, separated out white solid, and crude product methyl alcohol-tetrahydrofuran recrystallization, vacuum drying is obtained
Target product, yield is 67%.
Embodiment 4：The solid luminescent performance of the flame-retardant luminous bifunctional material (compound I) of difluorophenyl quinoline phosphine oxide is surveyed
Examination
Absorbed with HORIBA Jobin Yvon Aqualog and three-dimensional fluorescence scanning spectrometer determines difluorophenyl quinoline
The solid luminescent spectrum of the flame-retardant luminous bifunctional material (compound I) of phosphine oxide, excitation wavelength is 275nm, as a result sees Fig. 3.
From the figure 3, it may be seen that the solid powder of compound I, in the case where wavelength is for the ultraviolet excitation of 275nm, it is presented strong ultraviolet
Light is launched, and its emission peak is 360nm.Result illustrates that the compound is in solid-state with strong UV-light luminous characteristic.
Claims (7)
1. the difluorophenyl flame-retardant luminous bifunctional material of quinoline phosphine oxide shown in a kind of Formulas I：
2. the preparation method of the difluorophenyl flame-retardant luminous bifunctional material of quinoline phosphine oxide described in a kind of claim 1, it is special
Levy and be, comprise the following steps：It is 1 by mol ratio:0.8~1.2 2- cyclopropyl -4- (4- difluorophenyls) quinoline-3-formaldehyde
It is dissolved in organic solvent with double (p-methylphenyl) phosphine oxides, is stirred at reflux reaction 4~6 hours, rotary evaporation removes solvent, warp
Recrystallization, vacuum drying, obtain target product.
3. the preparation method of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide according to claim 1, it is special
Levy and be, the organic solvent is toluene or dioxane or toluene-methanol；Described recrystallization be using methyl alcohol or methyl alcohol-
Toluene, or methyl alcohol-tetrahydrofuran carries out recrystallization operation for solvent.
4. the application of the difluorophenyl flame-retardant luminous bifunctional material of quinoline phosphine oxide described in claim 1.
5. the application of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide according to claim 4, its feature exists
In being used for epoxy resin, polyester, polyamide flame retarded polymeric material or as additive flame retardant as reactive type fire retardant
Among engineering plastics.
6. the application of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide according to claim 4, its feature exists
In as ultra-violet light-emitting material for luminescent device, anti-fake material, fluorescent brightening, sensitive fluorescent field.
7. the application of the flame-retardant luminous bifunctional material of difluorophenyl quinoline phosphine oxide according to claim 4, its feature exists
In as light emitting-type fire retardant for fire-fighting, traffic, electronic apparatus, cable, plastics and synthetic fibers field.
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