CN107501526A - A kind of new DOPO types epoxy curing agent and preparation method thereof - Google Patents
A kind of new DOPO types epoxy curing agent and preparation method thereof Download PDFInfo
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- CN107501526A CN107501526A CN201710661306.5A CN201710661306A CN107501526A CN 107501526 A CN107501526 A CN 107501526A CN 201710661306 A CN201710661306 A CN 201710661306A CN 107501526 A CN107501526 A CN 107501526A
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- dopo
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- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 title abstract description 14
- 239000004593 Epoxy Substances 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000013067 intermediate product Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012467 final product Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 20
- 239000003822 epoxy resin Substances 0.000 abstract description 14
- 229920000647 polyepoxide Polymers 0.000 abstract description 14
- -1 (4 aminophenyl) (hydroxyl) methyl Chemical group 0.000 abstract description 12
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 abstract description 6
- 125000005842 heteroatom Chemical group 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229940125773 compound 10 Drugs 0.000 abstract 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 abstract 1
- 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 description 10
- 239000000243 solution Substances 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004079 fireproofing Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
-
- 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
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epoxy Resins (AREA)
- Fireproofing Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of new compound 10 ((4 aminophenyl) (hydroxyl) methyl) 9, oxide of 10 dihydro, 9 oxa-, 10 phospho hetero phenanthrene 10 and preparation method thereof, the compound is using DOPO and paranitrobenzaldehyde as raw material, reaction obtains intermediate product in ethanol or DMF solvent, intermediate product is reduced by iron powder again, neutralized purification obtains final product.The compound can be used not only as the curing agent of epoxy resin, while also can be used for its fire-retardant, and have the advantages that preparation process raw material be easy to get, preparation technology simplicity, be also convenient for popularization and application.
Description
Technical field
The present invention relates to epoxy curing agent technical field, and in particular to a kind of neo-epoxy resin curing agent 10-
Miscellaneous -10- phospho hetero phenanthrenes -10- oxides of ((4- aminophenyls) (hydroxyl) methyl) -9,10- dihydro-9-oxies and preparation method thereof.
Background technology
Epoxy resin has excellent mechanical performance, chemical resistance, electrical insulating property, processing characteristics, adhesive property, together
When because volatility is low in Curing Process of Epoxy do not generate small molecule, make its shrinkage low, in coating, adhesive, printing electricity
The field extensive use such as road plate, electronic package material, composite, Aero-Space and automobile.But the limit oxygen of epoxy resin
Index (LOI) only has 19.8%, holds fire hazardous, is restricted in many special dimensions.
Fire retardant from whether containing halogens halogen containing flame-retardant and halogen-free flame retardants can be divided into, wherein halogen containing flame-retardant because
There is excellent flame retardant effect to be once widely used as fire proofing for it, but because halogen fire proofing can produce during fire-retardant
Raw substantial amounts of smog and poisonous corrosive gas cause secondary hazards, thus gradually disabled；And halogen-free flame retardants can be effective
Promote the generation of stable intumescent char layer, suppress base material and continue that thermal oxidative reaction occurs, improve the thermal degradation temperature of curing system
Degree, mass loss temperature and coke growing amount, increasingly attract attention.Fire retardant from whether participate in reaction and response type can be divided into
Fire retardant and additive flame retardant, additive flame retardant price is less expensive, but compatibility, it is interface characteristics and it is dispersed etc. exist ask
Topic, can largely influence the mechanical property of material in itself；And though reactive flame retardant price is slightly higher, contained element is not easy
Migration, is not easy to ooze out, has excellent and permanent anti-flammability, smaller on the influence of polymeric material performance, and heat endurance is good.
Therefore, for solve epoxy resin when special dimension (such as printed circuit board (PCB), electronic package material) uses by
Limitation, a kind of non-halogen reacting fire-retardant epoxy curing agent can be designed and be introduced into epoxy resin, on the one hand played
The effect of crosslinking curing, on the other hand realize the effect of highly effective flame-retardant.
The content of the invention
An object of the present invention is to provide a kind of neo-epoxy resin curing agent 10- ((4- aminophenyls) (hydroxyl)
Methyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, its chemical structural formula is as follows：
Another object of the present invention is to provide the preparation method of above-mentioned neo-epoxy resin curing agent, including following step
Suddenly：Under protective atmosphere, DOPO and paranitrobenzaldehyde is set to react to obtain intermediate product in a solvent；By intermediate product and iron powder
It is added in acid solution, is neutralized after the completion of reaction with alkali, separating-purifying obtains final product.
According to such scheme, reactant paranitrobenzaldehyde and DOPO mol ratio are (1-1.5):1.
According to such scheme, the solvent is one kind in ethanol or N ' dinethylformamides (DMF).
According to such scheme, DOPO is 60-75 DEG C, reaction time 8-12h with paranitrobenzaldehyde reaction temperature, instead
It should complete through cooling down, filter, wash or rotate, and 80 DEG C of dry 24h obtain intermediate product.Reaction should not use high temperature, avoid pair
Nitrobenzaldehyde distils.
According to such scheme, intermediate product and iron powder are added in hydrochloric acid solution, reaction is stirred at room temperature, then uses hydrogen-oxygen
Change sodium solution to neutralize, purification is finally extracted with ethyl acetate and obtains final product.
According to such scheme, amino is converted into ensure that nitro is as much as possible, hydrochloric acid should be met：Intermediate product>6, iron
Powder：Intermediate product>3 mol ratio.
According to such scheme, the protective atmosphere is nitrogen.
The present invention is reacted with DOPO and paranitrobenzaldehyde, is obtained non-halogen reacting fire-retardant curing agent, be can be used in epoxy
The solidification of resin and fire-retardant.Compared with prior art, the invention has the advantages that：
1. a kind of new new compound 10- ((4- aminophenyls) (hydroxyl) methyl) -9 for having no report has been synthesized,
Miscellaneous -10- phospho hetero phenanthrenes -10- the oxides of 10- dihydro-9-oxies, in the epoxy its can both play crosslinking curing effect, again can be real
Existing halogen-free flameproof effect.
2. the nitro of strong electron-withdrawing group group is introduced into first step reaction, P in DOPO is set to be more easy to the carbon atom in attack carbonyl,
Greatly enhance reactivity.
3. the compound prepared is response type curing agent, can be reacted with cross linking of epoxy resin, therefore contained ignition-proof element is not
It is easy to migrate, it is not easy to ooze out, there is excellent and permanent anti-flammability, polymeric material performance is influenceed smaller.
4. the compatibility of the flame retardant curing agent and matrix resin is good, and raw material is cheap and easily-available, and reactions steps simple condition is easy
Control, yield is high, and solidification process is simple to operate, will have good application prospect in the solidification of epoxy resin and flame retardant area.
Brief description of the drawings
Fig. 1 is new compound 10- ((4- aminophenyls) (hydroxyl) methyl) -9,10- prepared by the embodiment of the present invention 1
The chemical shift figure of the miscellaneous -10- phospho hetero phenanthrenes -10- oxide structures of dihydro-9-oxy.
Fig. 2 is new compound 10- ((4- aminophenyls) (hydroxyl) methyl) -9,10- prepared by the embodiment of the present invention 1
Miscellaneous -10- phospho hetero phenanthrenes -10- the oxides of dihydro-9-oxy1H-NMR spectrum.
Embodiment
To make those of ordinary skill in the art fully understand technical scheme and beneficial effect, below in conjunction with specific
Embodiment is further described.
Chemical reaction involved by new compound building-up process of the present invention is as follows：
Reaction is carried out in two steps, and is reacted first by DOPO and paranitrobenzaldehyde under conditions of ethanol or DMF make solvent
Intermediate product is made, benzene nitro is reduced into anilino- by iron powder and hydrochloric acid, obtains final product by intermediate product.
Embodiment 1
(1) in N2Under atmosphere, to equipped with thermometer, condensing reflux, magnetic agitation and N2In 250 mL three-necked flasks being passed through
DOPO (0.01mol), paranitrobenzaldehyde (0.01mol) and ethanol (10 mL) are added, beginning to warm up and stirring makes it completely molten
Solution, then heats to 60 DEG C, in N28h is reacted under protection atmosphere.
(2) after question response terminates, it is cooled to room temperature, suction filtration obtains crude product, then with deionized water rinsing, is repeated 3 times, most
Dry 24h at 80 DEG C in vacuum drying chamber afterwards, obtain intermediate product.
(3) intermediate product (0.01mol), iron powder (0.035mol) and hydrochloric acid solution obtained by step (2) (are contained into 0.065mol
Hydrogen chloride) mixing, be stirred at room temperature just can react quickly, then add dilute NaOH solution neutralize, be extracted with ethyl acetate
Purification obtains final product.
Fig. 1 is new compound 10- ((4- aminophenyls) (hydroxyl) methyl) -9,10- two prepared by the embodiment of the present invention 1
Hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides1H-NMR spectrum, from hydrocarbon and coupled hydrocarbon of caused hydroxyl
Chemical shift, it can be verified that obtained product be 10- ((4- aminophenyls) (hydroxyl) methyl) -9,10- dihydro-9-oxies it is miscellaneous -
10- phospho hetero phenanthrene -10- oxides.
The product of 1 embodiment of table 11H-NMR spectrum resolution table
Embodiment 2
In N2Under atmosphere, to equipped with thermometer, condensing reflux, magnetic agitation and N2Add in the 250mL three-necked flasks being passed through
Enter DOPO (0.01mol), paranitrobenzaldehyde (0.015mol) and ethanol (10mL), beginning to warm up and stirring makes it completely molten
Solution, then heats to 60 DEG C, in N2Atmosphere under react 8h, subsequent step is the same as the step (2) in embodiment 1 and (3).
Embodiment 3
In N2Under atmosphere, to equipped with thermometer, condensing reflux, magnetic agitation and N2Add in the 250mL three-necked flasks being passed through
Enter DOPO (0.01mol), paranitrobenzaldehyde (0.015mol) and ethanol 10mL, beginning to warm up and stirring is completely dissolved it,
75 DEG C are then heated to, in N2Atmosphere under react 8h, subsequent step is the same as the step (2) in embodiment 1 and (3).
Embodiment 4
In N2Under atmosphere, to equipped with thermometer, condensing reflux, magnetic agitation and N2Add in the 250mL three-necked flasks being passed through
Enter DOPO (0.01mol), paranitrobenzaldehyde (0.015mol) and ethanol 10mL, beginning to warm up and stirring is completely dissolved it,
75 DEG C are then heated to, in N2Atmosphere under react 12h, subsequent step is the same as the step (2) in embodiment 1 and (3).
Application examples
Epoxy resin CYD127 is chosen, by its compound 10- ((4- aminophenyls) (hydroxyl) methyl) -9 with 10wt%,
Miscellaneous -10- phospho hetero phenanthrenes -10- the oxides of 10- dihydro-9-oxies, 1wt% DMP-30 or imidazoles (in terms of epoxy resin quality, under
Together), organic solvent DMF and filler are well mixed.It is pre- solid by the homemade silica gel mould of above-mentioned mixed liquor injection, being heated to 60 DEG C
Change 1h, be allowed to be molded.120 DEG C of solidification 2h are heated the mixture to, makes the abundant cured epoxy resin of curing agent, then proceedes to heat up
To 180 DEG C of solidify afterwards 2h, to eliminate the combination property that internal stress improves glue-joint strength and epoxy resin cured product.
Through analyzing contrast test, the compound 10- ((4- aminophenyls) (hydroxyl) methyl) -9,10- synthesized by the present invention
Miscellaneous -10- phospho hetero phenanthrenes -10- the oxides of dihydro-9-oxy are as curing agent, for more typical curing agent, fire resistance obtained compared with
Big lifting, UL94 flame retardant ratings are up to V-0 ranks, and limited oxygen index LOI is up to 27% or so.
Claims (8)
- A kind of 1. new compound, it is characterised in that the system of compounds be named as 10- ((4- aminophenyls) (hydroxyl) methyl)- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, its chemical structural formula are as follows：
- 2. the preparation method of new compound described in claim 1, it is characterised in that comprise the following steps：Under protective atmosphere, DOPO and paranitrobenzaldehyde is set to react to obtain intermediate product in a solvent；Intermediate product and iron powder are added in acid solution, Neutralized after the completion of reaction with alkali, separating-purifying obtains final product.
- 3. the preparation method of new compound according to claim 2, it is characterised in that：Reactant paranitrobenzaldehyde with DOPO mol ratio is (1-1.5):1.
- 4. the preparation method of new compound according to claim 2, it is characterised in that：The solvent is ethanol or N ' N- One kind in dimethylformamide.
- 5. the preparation method of new compound according to claim 2, it is characterised in that：DOPO is anti-with paranitrobenzaldehyde It is 60-75 DEG C, reaction time 8-12h to answer temperature, and reaction is completed through cooling down, filter, wash or rotate, and 80 DEG C of dryings 24h obtains intermediate product.
- 6. the preparation method of new compound according to claim 2, it is characterised in that：Intermediate product and iron powder are added Into hydrochloric acid solution, reaction is stirred at room temperature, is then neutralized with sodium hydroxide solution, purification is finally extracted with ethyl acetate and obtains most End-product.
- 7. the preparation method of new compound according to claim 2, it is characterised in that：Intermediate product is to final product In course of reaction, hydrochloric acid should be met：Intermediate product>6, iron powder：Intermediate product>3 mol ratio.
- 8. the preparation method of new compound according to claim 2, it is characterised in that：The protective atmosphere is nitrogen.
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| CN110698649A (en) * | 2019-06-28 | 2020-01-17 | 江西瀚泰新材料科技有限公司 | Ultraviolet-resistant flame-retardant epoxy resin curing agent and preparation thereof |
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| CN110698649A (en) * | 2019-06-28 | 2020-01-17 | 江西瀚泰新材料科技有限公司 | Ultraviolet-resistant flame-retardant epoxy resin curing agent and preparation thereof |
| CN110698649B (en) * | 2019-06-28 | 2022-07-08 | 江西瀚泰新材料科技有限公司 | Ultraviolet-resistant flame-retardant epoxy resin curing agent and preparation thereof |
| CN110511431A (en) * | 2019-09-03 | 2019-11-29 | 武汉工程大学 | A kind of nitrogen of the structure containing benzoguanamine-phosphorus system efficient flame-retarding agent and its synthesis and application |
| CN110511431B (en) * | 2019-09-03 | 2021-08-27 | 武汉工程大学 | Application of nitrogen-phosphorus efficient flame retardant containing benzoguanamine structure |
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