CN103936764B - N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines and preparation method thereof - Google Patents
N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines and preparation method thereof Download PDFInfo
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Abstract
The present invention is to provide a kind of N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines and preparation method thereof. Utilize substituted or non-substituted salicylide and 2,7-dihydroxy-9, the reaction of 9-pair-(4-aminophenyl) fluorenes, pass through again sodium borohydride reduction, obtain substituted or non-substituted adjacent hydroxy benzylamine base bisphenol fluorene, and then with fatty amine and paraformaldehyde through a step Mannich condensation reaction, obtain N-semiaromatic alkyl diamine-bisphenol type four degree of functionality benzoxazine monomers, course of reaction is simplified, and product total recovery improves; By adjusting rigidity and the flexible group in fatty amine and substituted or non-substituted salicylide compound, reduce the fusing point of benzoxazine monomer, crosslink density and the toughness of Polybenzoxazine are improved, solved have that the fluorenyl Polybenzoxazine molecular weight of larger space steric hindrance structure is little, crosslink density is low, problem that poor toughness and the introducing because of flexible group cause hot property to decline, improved the processing characteristics of polymer.
Description
Technical field
What the present invention relates to is a kind of high-molecular organic material, the present invention also relates to a kind of preparation method of high-molecular organic material.Specifically a kind of novel N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines and preparation method thereof.
Background technology
3,4-dihydro-1,3-benzoxazine (abbreviation benzoxazine) is to be raw material by amine, phenols and formaldehyde, through Mannich condensationThe class that reaction obtains is containing the 6-membered heterocyclic compound of O and N atom. As far back as 20 century 70s, Schreiber is just special at itIn profit, Dui benzoxazine oligomer modified epoxy is reported (Deutsche Bundespatent 2217099, " PhenolicresinaselectricInsulator "). The eighties in 20th century, first Higginbottom has found polyfunctionality benzo in the research of doing coating materialCross-linking reaction (the United States Patent (USP) 4501864, " Polymerizablecompositionscomprisingpolyaminesand of oxazinePoly (dihydrobenzoxazines) "). 1994, Ishida and Ning completed the performance study (Ning of p-poly-phenyl Bing oxazine at firstX,IshidaH.Phenolicmaterialsviaring-openingpolymerization-synthesisandcharacterizationofbisphenol-Abasedbenzoxazinesandtheirpolymers.JPolymSciAPolymChem,1994,32:1121-1129). Find by a large amount of research, Polybenzoxazine resin is performance the same as phenolic aldehyde, epoxy and maleimideExcellent novel hot setting resin. Benzoxazine monomer can form three-dimensional net structure by self ring-opening polymerisation, while solidifying without littleMolecule discharges, and goods porosity is low, and its volume approximate zero is shunk, and has high glass transition temperature (Tg) and heat endurance,Good mechanical performance, electric property, fire resistance and high carbon yield, can be applicable to advanced composite material matrix resin, electronicsThe fields such as encapsulation, adhesive, insulating materials.
At present, the approach that improves Polybenzoxazine resin property mainly comprises three kinds: the one, and strong according to benzoxazine MOLECULE DESIGNFeature, adopt different He An sources, phenol source, synthesize novel benzoxazine monomer, can meet different application thereby prepareThe material that occasion needs; The 2nd, use the Dui Ben Bing Evil such as some general thermoplastic resins, thermosetting resin, rubber, elastomerPiperazine carries out blending and modifying research; The 3rd, by introducing second component, make it dispersed in benzoxazine colophony, prepare treeResin-based composite, finally reaches modification object. Under normal circumstances, in molecular structure, introduce flexible alkyl or alkoxyl,Can reduce the fusing point of monomer, thereby improve toughness and the processing characteristics of polymer, but often cause polymer hot property greatly underFall; And introducing rigid radical, although can improve the hot property of polymer, can cause the increase of polymer fragility and high solidifyingTemperature. Therefore, how solving this contradiction is the key that obtains high-performance poly benzoxazine colophony.
In recent years, along with deepening continuously that kind, synthetic method and the catalytic polymerization of benzoxazine monomer are studied, polyfunctionality benzeneBing oxazine has caused many researchers' concern. As LinCH etc. has synthesized phosphorous triphenol and triamine type benzoxazine monomer (LinCH,CaiSX,LeuTS,etal.Synthesisandpropertiesofflame-retardantbenzoxazinesbythreeapproaches.JPolymSciAPolymChem,2006,44:3454–3468P;ChangCW,LinCH,LinHT,etal. Developmentofanaromatictriamine-basedflame-retardantbenzoxazineanditshigh-performanceCopolybenzoxazines.EurPolymJ, 2009,49:680-689P), the T of polymergBe respectively 220 and 242 DEG C, justBeginning heat decomposition temperature (T5) be 324 and 349 DEG C, 800 DEG C of carbon yield (Yc) reach 48% and 58%. WuX etc. have prepared threePolyphosphazene base four degrees of functionality and six degree of functionality benzoxazine monomer (WuX, LiuSZ, TianDT, etal.Highlybranchedbenzoxazinemonomerbasedoncyclotriphosphazene:Synthesisandpropertiesofthemonomerandpolybenzoxazines.Polymer,2011,52:1004-1012P;WuX,LiuSZ,TianDT,etal.Well-definedorganic–inorganichybridbenzoxazinemonomersbasedoncyclotriphosphazene:Synthesis,Propertiesofthemonomersandpolybenzoxazines.Polymer, 2011,52:4235-4245P), PolybenzoxazineTgBe respectively 254 DEG C and 152 DEG C, T5It is 442 DEG C and 403 DEG C. But, at present these all research work be all based onFull phenol type and full amine type benzoxazine monomer, taking polyhydric phenols or polyamine based compound as raw material, anti-by Mannich condensationAnswer and make. The synthetic method of this type of monomer can obtain target product by single step reaction, two-step reaction or three-step reaction, closesOne-tenth process is relatively simple. In addition, the full phenol type of analog structure and full amine type Polybenzoxazine due to polymer network structure notWith, its performance also has certain difference, and under normal circumstances, the performance of amine type Polybenzoxazine is higher than phenol type Polybenzoxazine. ButFull phenol type and full amine type benzoxazine can only be by polyhydric phenols (as bisphenol-A etc.) or polyamines (as MDA etc.) pointNot do not react with monoamine (as aniline etc.) or single phenol (as phenol etc.), restricted to a great extent benzoxazine moleculeDesignability, makes the performance regulation and control of this type of Polybenzoxazine resin be subject to great restriction.
Fluorenes has rigid plane biphenyl structural, wide energy gap, high-luminous-efficiency, good heat endurance, photostability, chemistry is steadyQualitative and be easy to the performances such as processing. Fluorenes molecule is introduced in benzoxazine monomer structure, can be made into a series of have good thermally-stabilisedThe benzoxazine colophony of property, humidity resistance, dielectric properties, mechanical performance. Wherein, bisphenol fluorene-anilino-, diamine fluorenes-phenolThe T of base PolybenzoxazinegBe respectively 229 and 253 DEG C, T5Be respectively 334 and 400 DEG C, YcReach 51% and 49%(see literary compositionOffer JunWang, Ming-qingWu, Wen-binLiu, etal.Synthesis, curingbehaviorandthermalpropertiesoffluorenecontainingbenzoxazines.EuropeanPolymerJournal,2010,46:1024–1031；JunWang,Xuan-YuHe,Jun-TingLiu,etal.InvestigationofthePolymerizationBehaviorandRegioselectivityOfFluoreneDiamine-BasedBenzoxazines.Macromol.Chem.Phys.2 013,214,617-628). But,Fluorenyl benzoxazine in above-mentioned example all belongs to conventional bis-phenol and diamine type, and fluorenes molecule is to be present in pendant groups formIn polymer architecture, cause the fragility of polymer large, poor toughness, adds that monomer fusing point is high, is difficult to machine-shaping, thereby restrictionThis resinoid further application.
The synthetic method of traditional bisphenol type or diamine type benzoxazine monomer is fairly simple, by aromatic amine or fatty amine and aldehydeThere is Mannich condensation reaction with phenol, thus Xing Cheng oxazine ring. For 2,7-dihydroxy-9,9-pair-(4-aminophenyl) fluorenes (is abbreviated asBis-phenol-diamine fluorenes), in molecule, contain 2 phenolic hydroxyl groups and 2 amino, by traditional Mannich condensation reaction simultaneouslyBe difficult to obtain target product. When adopting first by amido protecting, then carry out Mannich condensation reaction with fatty amine, obtain fatAmido bisphenol type benzoxazine. But in amino deprotection process, fatty amido oxazine ring is very unstable, and open loop very easily occursReaction, causes obtaining target product.
Summary of the invention
The object of the present invention is to provide a kind of N-semiaromatic alkyl pair that simultaneously contains bisphenol type and diamine type in molecular structurePhenol-diamine type four degree of functionality fluorenyl benzoxazines. The present invention also aims to provide a kind of N-semiaromatic alkyl bis-phenol-diamine typeThe preparation method of four degree of functionality fluorenyl benzoxazines.
N-semiaromatic alkyl bis-phenol-diamine type of the present invention four degree of functionality fluorenyl benzoxazines have following structural formula:
Wherein: R1For-H ,-CH3、－OCH3,-F ,-Cl or-one in Br, R2For-CnH2n+1And n=1～12,－CH2CH=CH2、－CH2C ≡ CH orIn one.
The preparation method of N-semiaromatic alkyl bis-phenol-diamine type of the present invention four degree of functionality fluorenyl benzoxazines is:
(1) 2,7-dihydroxy-9,9-is two-(4-aminophenyl) fluorenes synthetic
2,7-dihydroxy-9-Fluorenone, aniline and trifluoromethayl sulfonic acid are joined in container successively to 2,7-dihydroxy-9-Fluorenone and benzeneThe mol ratio of amine is 1:6～10, and the mol ratio of 2,7-dihydroxy-9-Fluorenone and trifluoromethayl sulfonic acid is 1:0.1～0.5, reaction temperatureBe 130～180 DEG C, under nitrogen atmosphere, react 8～12h, be then cooled to room temperature, product is poured the NaOH of 20g/L intoIn ethanolic solution, precipitation is after filtration, ethanol washes, vacuum drying, obtains 2,7-dihydroxy-9, and 9-is two-(4-aminophenyl) fluorenes M-1Represent;
(2) substituted or non-substituted adjacent hydroxy benzylamine base bisphenol fluorene is synthetic
M-1, substituted or non-substituted salicylide, sulfuric acid and ethanol are joined in packaging container successively to M-1 and substituted or non-substitutedThe mol ratio of salicylide is 1:2, and the mol ratio of M-1 and sulfuric acid is 5:1, under agitation adds hot reflux 4～10h, after reaction finishesBe cooled to room temperature, add sodium borohydride, the mol ratio of sodium borohydride and M-1 is 3:1, continues to stir 5min, adds water and dichloroMethane, washs organic phase with distilled water, removes carrene through rotary evaporation, obtains 2,7-dihydroxy-9, and 9-is two-and (4-(replaces or non-Replace adjacent hydroxy benzylamine base) phenyl) fluorenes M-2 represents;
(3) N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines is synthetic
In reactor, add M-2, fatty amine, paraformaldehyde and organic solvent, M-2, fatty amine and paraformaldehyde moleThan for 1:2:6, at 60～140 DEG C, react 12～48h, be cooled to room temperature, organic solvent is removed in decompression distillation, with ether dissolution,After NaOH washing, washing, isolate organic phase, rotary evaporation is except desolventizing, and vacuum drying, obtains N-semiaromatic alkylBis-phenol-diamine type four degree of functionality fluorenyl benzoxazines represent with BF-pa.
The preparation method of N-semiaromatic alkyl bis-phenol-diamine type of the present invention four degree of functionality fluorenyl benzoxazines can also comprise:
1, described substituted or non-substituted salicylide is Benzaldehyde,2-hydroxy, 4-methyl-Benzaldehyde,2-hydroxy, 4-methoxyl group-2-hydroxylBenzaldehyde, 5-methoxyl group-Benzaldehyde,2-hydroxy, the fluoro-Benzaldehyde,2-hydroxy of 5-, the fluoro-Benzaldehyde,2-hydroxy of 4-, 5-chlorine-2-hydroxyl benzene firstOne in the bromo-Benzaldehyde,2-hydroxy of aldehyde or 5-.
2, described fatty amine is methylamine, ethamine, butylamine, hexylamine, octylame, decyl amine, dodecyl amine, allyl amine, alkynes thirdOne in base amine or cyclohexylamine.
3, described organic solvent is the mixed solvent of a kind of composition in chlorobenzene and toluene, dimethylbenzene, dioxane or chloroform,Both volume ratios are 1:1～10.
The invention provides a kind of N-semiaromatic alkyl bis-phenol with good fire resistance, heat resistance and wet-hot aging performance-Diamine type four degree of functionality fluorenyl Polybenzoxazine resins. By adjusting rigidity and the flexible group in fatty amine and phenolic compound,To reduce the fusing point of benzoxazine monomer, improve crosslink density and the toughness of Polybenzoxazine, solve and there is larger space steric hindrance knotThe fluorenyl Polybenzoxazine molecular weight of structure is little, crosslink density is low, poor toughness and the introducing because of flexible group cause hot property to declineProblem, improve the processing characteristics of polymer, the structure and the performance that realize Polybenzoxazine are controlled, expand fluorenyl benzoxazine treeFat application.
N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl Polybenzoxazine structural characterizations of the present invention utilize infrared spectrum(Spotlight100, PE company of the U.S.) and nuclear magnetic resonance spectrometer (AVANCE-500, Switzerland Bruker), infrared spectrum is surveyedPilot production pellet technique, Sample Scan 4 times, resolution ratio 4cm-1, sweep limits to 4000～500cm-1, nuclear magnetic resonanceHydrogen spectrum is mark in doing with tetramethylsilane (TMS), and deuterated dimethyl sulfoxide (DMSO) is made solvent. Polymer performance testAdopt differential scanning calorimeter (DSC, TA company of the U.S.) and thermogravimetric analyzer (TGA, TA company of the U.S.), nitrogenAtmosphere, heating rate is 10 DEG C/min.
The present invention has developed a kind of synthetic route of simple while Sheng Cheng oxazine ring, utilizes substituted or non-substituted salicylide and ammoniaRadical reaction, by sodium borohydride reduction, obtains substituted or non-substituted adjacent hydroxy benzylamine base bisphenol fluorene, and then with fatty amine and manyPolyformaldehyde, through Mannich condensation reaction, can obtain bis-phenol-diamine type four degree of functionality benzoxazine monomers, and course of reaction obtains letterChange, product total recovery improves. By the rigidity in monomer structure and the regulation and control of flexible group, improve the crosslinked close of PolybenzoxazineDegree and toughness, solve have that the fluorenyl Polybenzoxazine molecular weight of larger space steric hindrance structure is little, crosslink density is low, poor toughness withAnd cause the problem of hot property degradation because of the introducing of flexible group. N-semiaromatic alkyl bis-phenol-diamine type four that the present invention obtainsDegree of functionality fluorenyl Polybenzoxazine resin has good heat endurance, mechanical performance and low hygroscopicity, can be used for manufacturing highPerformance structure material, electronic package material, high-temperature Resistance Adhesives, ablation resistant material, resistant material etc., be widely used in electricityThe fields such as son, Aero-Space, machine-building.
Brief description of the drawings
Fig. 1 is the synthetic route chart of N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, is necessary to be pointed out that at this, the embodiment of the present invention is only for rightThe present invention is further described, but can not be interpreted as limiting the scope of the invention, person skilled in the art's root in this fieldMake some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
(1) 2,7-dihydroxy-9,9-is two-(4-aminophenyl) fluorenes synthetic
By 0.05mol2,7-dihydroxy-9-Fluorenone, 0.40mol aniline and 0.015mol trifluoromethayl sulfonic acid join successively withIn the four-hole boiling flask of stirring rotator, condenser pipe, thermometer and gas access, pass into nitrogen, at 150 DEG C, react 10h, soAfter be cooled to room temperature, product is poured in the NaOH ethanolic solution that 100mL concentration is 5g/L, precipitation after filtration, ethanol washes,Vacuum drying, obtains 2,7-dihydroxy-9, and 9-pair-(4-aminophenyl) fluorenes (M-1), yield is 92.3%.
(2) substituted or non-substituted adjacent hydroxy benzylamine base bisphenol fluorene is synthetic
0.02molM-1,0.04mol2-hydroxy benzaldehyde, 0.004mol sulfuric acid and 150mL ethanol are joined stirring is housedIn the there-necked flask of device, condenser pipe, thermometer, heating reflux reaction 8h, is cooled to room temperature after reaction finishes, and adds 0.06molSodium borohydride, then continues to stir 5min, adds water, and with dichloromethane extraction, repeatedly washing, finally isolates organic phase, revolvesTurn evaporation except desolventizing, obtain 2,7-dihydroxy-9,9-pair-(4-(2-hydroxyl-benzamido group) phenyl) fluorenes (M-2), yield 86.4%.
(3) N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines is synthetic
In 100mL there-necked flask, add respectively 0.01mol butylamine, 0.03mol paraformaldehyde, 0.005molM-2,40mLDioxane and 10mL chlorobenzene, at 110 DEG C of reaction 24h, be then cooled to room temperature, and decompression distillation, except desolventizing, obtainsCrude product dissolves with carrene, by 0.5mol/L sodium carbonate liquor and distilled water washing organic phase, adds anhydrous sodium sulfate dryingSpend the night, filter, filtrate is through rotary evaporation except desolventizing, and vacuum drying, obtains the derivative N-semiaromatic alkyl of salicylide-butylamine twoPhenol-diamine type four degree of functionality fluorenyl benzoxazine monomers, fusing point (Tm) be 104 DEG C, yield 84.5%.
Proton nmr spectra test result (500M, CDCl3，ppm）：6.53～7.47（m，20H，Ar-H），5.37And 4.76(d, 8H, is respectively the fluorenes ring O-CH on oxazine ring that is connected with phenyl ring2-N), 4.58 and 3.83(d, 8H, respectivelyFor the fluorenes ring Ar-CH on oxazine ring that is connected with phenyl ring2-N），2.71（t，4H，N-CH2-), 1.53 and 1.24(m, 8H,-CH2-），0.92（t，6H，-CH3); Examination of infrared spectrum result (FT-IR, KBr, cm-1, as follows): 1506(1,2,4,5-The characteristic absorption peak of four substituted benzenes), 1379(methyl C-H out-of-plane bending vibration), on 1321(oxazine ring, waving of methylene shakenMoving), 1252 are respectively be connected with the phenyl ring asymmetric stretching vibration of C-O-C on oxazine ring of fluorenes ring with 1226(), 1156(the asymmetric stretching vibration peak of C-N-C key), 1077 and 1033(C-O-C symmetrical stretching vibration), 931～951(is respectivelyFor C-H out-of-plane bending vibration on the oxazine ring that is connected with phenyl ring with fluorenes ring, be also the characteristic peak of phenyl ring Dai You oxazine ring). In conjunction withProton nmr spectra and infrared spectrum confirm that products therefrom is target monomer.
Benzoxazine monomer is put into electric drying oven with forced convection, adopt programmed temperature method to carry out heat cure, curing cycle to monomerFor: 180 DEG C/2h, 200 DEG C/2h, 220 DEG C/2h, 240 DEG C/2h, finally obtain curing Polybenzoxazine resin, through DSC andTGA test, the T of Polybenzoxazine resing：338，T5：353，Yc：42%。
Embodiment 2
Except the Benzaldehyde,2-hydroxy in synthesis step (2) changes the fluoro-Benzaldehyde,2-hydroxy of 4-into, reflux time changes 6 into by 8hH, the butylamine in synthesis step (3) changes octylame into, and solvent changes 30mL first into by 40mL dioxane and 10mL chlorobenzeneBenzene and 20mL chlorobenzene, the reaction time is changed into outside 12h by 24h, and other conditions, with embodiment 1, finally obtain 4-fluorine bigcatkin willowN-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazine monomers that aldehyde-octylame is derivative, TmBe 68 DEG C, yield69.3%(calculates taking the yield of synthesis step 2～5 as benchmark, as follows).
1HNMR:6.58～7.37(m, 18H, Ar-H), 5.33 and 4.73(d, 8H, is respectively on fluorenes ring and phenyl ringO-CH2-N), 4.55 and 3.94(d, 8H, is respectively Ar-CH on fluorenes ring and phenyl ring2-N），2.68（t，4H，N-CH2-），1.54 and 1.21(m, 24H ,-CH2-），0.86（t，6H，-CH3); FT-IR:1508,1382,1368 and 1317,1251 and 1223,1155,1101(C-F stretching vibration), 1076,928～953 and 729(long-chain fat hydrocarbon C-H waveVibration).
Condition of cure is with embodiment 1, the T of Polybenzoxazine resing：321℃，T5：361℃，Yc：46%。
Embodiment 3
Except the Benzaldehyde,2-hydroxy in synthesis step (2) changes 4-methoxyl group-Benzaldehyde,2-hydroxy into, the fourth in synthesis step (3)Amine changes cyclohexylamine into, and solvent changes 45mL dimethylbenzene and 5mL chlorobenzene into by 40mL dioxane and 10mL chlorobenzene, reactionTemperature changes 140 DEG C into by 110 DEG C, and the reaction time is changed into outside 12h by 24h, and other conditions, with embodiment 1, finally obtainN-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazine monomers that 4-methoxysalicylaldehyde-cyclohexylamine is derivative, TmFor112 DEG C, yield 77.8%.
1HNMR:6.53～7.32(m, 18H, Ar-H), 5.34 and 4.85(d, 8H, is respectively on fluorenes ring and phenyl ringO-CH2-N), 4.56 and 4.05(d, 8H, is respectively Ar-CH on fluorenes ring and phenyl ring2-N），3.45（s，6H，O-CH3），2.52（m，2H，N-CH-），1.05～1.86（m，20H，-CH2-）；FT-IR：1505、1387、1370、1326、1254,1225,1078,1153 and 928～956.
Condition of cure is with embodiment 1, the T of Polybenzoxazine resing：328℃，T5：363，Yc：43%。
Embodiment 4
Except the 4-methoxyl group-Benzaldehyde,2-hydroxy in synthesis step (2) changes Benzaldehyde,2-hydroxy into, the ring in synthesis step (3)Hexylamine changes allyl amine into, and other conditions, with embodiment 3, finally obtain the derivative N-semiaromatic alkyl bis-phenol of salicylide-allylamine-diamine type four degree of functionality fluorenyl benzoxazine monomers, TmBe 113 DEG C, yield 83.3%.
1HNMR：6.62～7.31（m，20H，Ar-H），5.79（m，2H，-CH=），5.11～5.20（m，4H，-CH=CH2), 5.36 and 4.76(d, 8H, is respectively O-CH on fluorenes ring and phenyl ring2-N), 4.57 and 3.95(d, 8H,Be respectively Ar-CH on fluorenes ring and phenyl ring2-N），3.27（d，4H，-CH2-); FT-IR:3084(=C-H stretching vibration),1644(C=C stretching vibration), 1508,1370,1323,1255,1223,1155,1076,989 and 910(=C-HThe outer deformation vibration of face) and 929～951.
The heat cure system of the derivative benzoxazine monomer of salicylide-allylamine is: 180 DEG C/2h, and 200 DEG C/2h, 220 DEG C/2h,240 DEG C/2h, 260 DEG C/2h, finally obtain the T of Polybenzoxazineg：363，T5：384，Yc：58%。
Embodiment 5
Except the cyclohexylamine in synthesis step (3) changes ethamine into, other conditions, with embodiment 3, finally obtain 4-methoxysalicylaldehydeN-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines that-ethamine is derivative, TmBe 125 DEG C, yield 76.0%.
1HNMR:6.61～7.42(m, 18H, Ar-H), 5.42 and 4.81(d, 8H, is respectively on fluorenes ring and phenyl ringO-CH2-N), 4.63 and 3.92(d, 8H, is respectively Ar-CH on fluorenes ring and phenyl ring2-N），3.43（s，6H，-O-CH3），2.69（m，4H，-CH2-），1.05（t，6H，-CH3）；FT-IR：1505、1386、1368、1320、1260、1228、1153,1071 and 929～961.
Condition of cure is with embodiment 1, the T of Polybenzoxazine resing：342℃，T5：375℃，Yc：48%。
The present invention, by a step Mannich condensation reaction, has obtained the N-semiaromatic that simultaneously contains diamine type and bisphenol type in moleculeAlkyl four degree of functionality fluorenyl benzoxazine monomers. And the curing reaction temperature of Shuan Fen Xing oxazine ring is lower than diamine Xing oxazine ring, open loopCan there is open loop by catalysis diamine type oxazine ring in the phenolic hydroxyl group of rear generation, thereby reduced benzoxazine on the whole at lower temperatureThe solidification temperature of monomer. The increase of You Yu oxazine number of rings amount, has improved the rigidity of Polybenzoxazine and the crosslink density of polymer,Therefore the Polybenzoxazine that obtained has higher heat decomposition temperature, higher glass transition temperature and higher carbon yield,And solved have that the fluorenyl Polybenzoxazine molecular weight of larger space steric hindrance structure is little, crosslink density is low, poor toughness and because of softThe introducing of property group causes a difficult problem for hot property degradation. Wherein, the glass transition temperature of Polybenzoxazine has all exceeded300 DEG C. Meanwhile, by the regulation and control of rigidity and flexible group, not only reduce the melt temperature of monomer, improved processing characteristics,The toughness that has simultaneously improved Polybenzoxazine, has reduced fragility, can be used for manufacturing high performance structures material, electronic package material,High-temperature Resistance Adhesives, ablation resistant material, resistant material etc., have extensively in fields such as electronics, Aero-Space, machine-buildingApplication prospect.
Claims (5)
1. a preparation method for N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines, is characterized in that:
(1) 2,7-dihydroxy-9,9-is two-(4-aminophenyl) fluorenes synthetic
2,7-dihydroxy-9-Fluorenone, aniline and trifluoromethayl sulfonic acid are joined in container successively to 2,7-dihydroxy-9-Fluorenone and benzeneThe mol ratio of amine is 1:6～10, and the mol ratio of 2,7-dihydroxy-9-Fluorenone and trifluoromethayl sulfonic acid is 1:0.1～0.5, reaction temperatureBe 130～180 DEG C, under nitrogen atmosphere, react 8～12h, be then cooled to room temperature, product is poured the NaOH of 20g/L intoIn ethanolic solution, precipitation is after filtration, ethanol washes, vacuum drying, obtains 2,7-dihydroxy-9, and 9-is two-(4-aminophenyl) fluorenes M-1Represent;
(2) substituted or non-substituted adjacent hydroxy benzylamine base bisphenol fluorene is synthetic
M-1, substituted or non-substituted salicylide, sulfuric acid and ethanol are joined in packaging container successively to M-1 and substituted or non-substitutedThe mol ratio of salicylide is 1:2, and the mol ratio of M-1 and sulfuric acid is 5:1, under agitation adds hot reflux 4～10h, after reaction finishesBe cooled to room temperature, add sodium borohydride, the mol ratio of sodium borohydride and M-1 is 3:1, continues to stir 5min, adds water and dichloroMethane, washs organic phase with distilled water, removes carrene through rotary evaporation, obtains 2,7-dihydroxy-9, and 9-is two-and (4-(replaces or non-Replace adjacent hydroxy benzylamine base) phenyl) fluorenes M-2 represents;
(3) N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines is synthetic
In reactor, add M-2, fatty amine, paraformaldehyde and organic solvent, M-2, fatty amine and paraformaldehyde moleThan for 1:2:6, at 60～140 DEG C, react 12～48h, be cooled to room temperature, organic solvent is removed in decompression distillation, with ether dissolution,After NaOH washing, washing, isolate organic phase, rotary evaporation is except desolventizing, and vacuum drying, obtains N-semiaromatic alkylBis-phenol-diamine type four degree of functionality fluorenyl benzoxazines represent with following structural formula:
Wherein: R1For-H ,-CH3、－OCH3,-F ,-Cl or-one in Br, R2For-CnH2n+1And n=1～12,－CH2CH＝CH2、－CH2C ≡ CH orIn one.
2. the preparation method of N-semiaromatic alkyl bis-phenol-diamine type according to claim 1 four degree of functionality fluorenyl benzoxazines,It is characterized in that: described substituted or non-substituted salicylide is Benzaldehyde,2-hydroxy, 4-methyl-Benzaldehyde,2-hydroxy, 4-methoxyl group-2-Hydroxy benzaldehyde, 5-methoxyl group-Benzaldehyde,2-hydroxy, the fluoro-Benzaldehyde,2-hydroxy of 5-, the fluoro-Benzaldehyde,2-hydroxy of 4-, 5-chlorine-2-hydroxylOne in the bromo-Benzaldehyde,2-hydroxy of benzaldehyde or 5-.
3. the preparation of N-semiaromatic alkyl bis-phenol-diamine type according to claim 1 and 2 four degree of functionality fluorenyl benzoxazinesMethod, is characterized in that: described fatty amine is methylamine, ethamine, butylamine, hexylamine, octylame, decyl amine, dodecyl amine, allylOne in base amine, propargyl amine or cyclohexylamine.
4. the preparation of N-semiaromatic alkyl bis-phenol-diamine type according to claim 1 and 2 four degree of functionality fluorenyl benzoxazinesMethod, is characterized in that: described organic solvent is a kind of composition in chlorobenzene and toluene, dimethylbenzene, dioxane or chloroformMixed solvent, both volume ratios are 1:1～10.
5. the preparation method of N-semiaromatic alkyl bis-phenol-diamine type according to claim 3 four degree of functionality fluorenyl benzoxazines,It is characterized in that: it is molten with mixing of a kind of composition in toluene, dimethylbenzene, dioxane or chloroform that described organic solvent is chlorobenzeneAgent, both volume ratios are 1:1～10.
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| CN105061464B (en) * | 2015-07-30 | 2017-05-24 | 哈尔滨工程大学 | Monophenol-diamine type asymmetric tri-functionality quinoxalinyl benzoxazine and preparation method thereof |
| CN105061466B (en) * | 2015-09-01 | 2017-06-20 | 哈尔滨工程大学 | Main chain bisphenol type quinoxalinyl benzoxazine and preparation method thereof |
| FR3045605B1 (en) * | 2015-12-16 | 2023-10-27 | Michelin & Cie | HALOGENATED BENZOXAZINE USABLE FOR THE SYNTHESIS OF POLYBENZOXAZINE |
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