CN105061464B - Monophenol-diamine type asymmetric tri-functionality quinoxalinyl benzoxazine and preparation method thereof - Google Patents
Monophenol-diamine type asymmetric tri-functionality quinoxalinyl benzoxazine and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a monophenol-diamine type asymmetric tri-functionality quinoxalinyl benzoxazine and a preparation method thereof. The method includes: taking m-dinitrobenzil and 4-hydroxy-o-phenylenediamine as the raw materials to synthesize a quinoxaline intermediate containing one phenolic hydroxyl group and two nitro groups, conducting catalytic reduction to obtain monophenol hydroxy and diaminoquinoxaline, then carrying out reaction with salicylaldehyde to generate a quinoxaline triphenol compound containing an iminomethyl group, conducting reduction by sodium borohydride, and then carrying out ring-closure reaction with primary amine and paraformaldehyde, thus obtaining a monophenol-diamine type asymmetric tri-functionality quinoxalinyl benzoxazine monomer. By means of the excellent heat resistance of the quinoxaline molecule itself, the method introduces a flexible alkyl chain and a polymerizable group to make the monomer have low melting point and additional polymerization crosslinking site, thereby improving the processability, and with the introduction of more oxazine rings, the polybenzoxazine resin thereof shows excellent heat resistance and good mechanical properties, and can be used for manufacturing high performance structural materials and the like.
Description
Technical field
The present invention relates to a kind of high-molecular organic material, the present invention also relates to a kind of preparation of high-molecular organic material
Method.Specifically a kind of new single asymmetric three-functionality-degree quinoxalinyl benzoxazine of the amine type of phenol-two and preparation method thereof.
Background technology
Benzoxazine is a kind of compound obtained through Mannich condensation reactions by phenolic compound, formaldehyde and primary amine, can
There is ring-opening polymerisation under being acted in heating or Louis acid catalysis, the cured product similar in construction to phenolic resin is formed,
It is a kind of new phenolic resin.This resin in addition to the heat resistance and anti-flammability excellent with phenolic resin, also certain
The fragility and dimensional instability of phenolic resin are improved in degree.Its most significant advantage is formed by itself ring-opening polymerisation
Three-dimensional net structure, is discharged during solidification without small molecule, and product porosity is low, and its volume approximate zero is shunk, and has geometry heat high steady
Qualitative and good mechanical performance, electric property, fire resistance and Residual carbon high.These excellent performances cause benzo
Oxazine is in fields such as advanced composite matrix resin, Electronic Packaging, adhesive, fire proofing, ablation resistant material, insulating materials
It is widely used.In recent years, with deepening continuously that the species of benzoxazine monomer, synthetic method and catalytic polymerization are studied,
Polyfunctionality benzoxazine has caused the concern of many researchers.Such as woods celebrating is dazzled and has synthesized phosphorous triphenol and three amine type benzene and Evil
Piperazine monomer, the T of polymergRespectively 220 and 242 DEG C, initial pyrolyzation temperature (T5) it is 324 and 349 DEG C, 800 DEG C of carbon yields reach
48% and 58% (Lin CH, Cai1SX, Leu TS, Hwang TY, Lee HH.Synthesis and properties of
flame-retardant benzoxazines by three approaches.J Polym Sci A Polym Chem,
2006,44:3454-3468P；Chang CW,Lin CH,Lin HT,Huang HJ,Tu AP.Development of an
aromatic triamine-based flame-retardant benzoxazine and its high-performance
copolybenzoxazines.Eur Polym J,2009,49:680-689P).Liu Chengmei etc. is prepared for the official of tripolyphosphazene base four
Energy degree and six degree of functionality benzoxazine monomers, the T of its PolybenzoxazinegRespectively 254 DEG C and 152 DEG C, T5Respectively 442 DEG C and
403 DEG C, due to being crosslinked the increase of position, the hot property and fire resistance of polymer greatly improve (Wu X, Liu SZ, Tian DT,
Qiu JJ,Liu CM.Highly branched benzoxazine monomer based on
cyclotriphosphazene:Synthesis and properties of the monomer and
polybenzoxazines.Polym,2011,52:1004-1012P；Wu X,Liu SZ,Tian DT,Qiu JJ,Liu
CM.Well-defined organic–inorganic hybrid benzoxazine monomers based on
cyclotriphosphazene:Synthesis,properties of the monomers and
polybenzoxazines.Polym,2011,52:4235-4245P).In addition, also with triazine structure, POSS structures etc.
It is the report of the polyfunctionality benzoxazine monomer of basic skeleton structure.But the above-mentioned benzoxazine monomer overwhelming majority belongs to symmetrical
Oxazine ring structure.
Quinoxaline is a kind of heterocyclic compound, is condensed with a pyrazine ring by a phenyl ring and formed, and 2,3,6 can introduce
Various active group, with very flexible MOLECULE DESIGN, can be used to synthesize polyphenylene quinoxaline, quinoxalinyl polyamides Asia
The polymer such as amine, polyethers, polyester.At the same time, this quinoxaline structure have bond energy higher, huge molal volume and
Weaker polarity, impart the excellent heat-resisting and thermo oxidative stability of such polymer, resistance to environmental stability, low-k with
Dielectric loss, in organic solvent good dissolubility and good mechanical property.
The content of the invention
It is an object of the invention to provide it is a kind of with excellent hot property, mechanical property and good processing characteristics and
The asymmetric three-functionality-degree quinoxalinyl benzoxazine of single amine type of phenol-two of toughness.It is a kind of single the present invention also aims to provide
The preparation method of the asymmetric three-functionality-degree quinoxalinyl benzoxazine of the amine type of phenol-two.
The object of the present invention is achieved like this：
The asymmetric three-functionality-degree quinoxalinyl benzoxazine of single amine type of phenol-two of the invention has following structure：
In formula, R1It is H, CH3Or OCH3In one kind, R2It is C2~C12Alkyl, pi-allyl, propargyl or furans methylene
One kind in base.
The preparation method of the asymmetric three-functionality-degree quinoxalinyl benzoxazine of single amine type of phenol-two of the invention is：
(1) to addition m-dinitrobenzil, 4- hydroxyls o-phenylenediamine and glacial acetic acid in container, wherein, MDNB
The mol ratio of even acyl and 4- hydroxyl o-phenylenediamines is 1:1~1.2, mixture reacts 4~8h at a reflux temperature, is subsequently cooled to
Room temperature, filtering, filter cake drying, gained crude product is recrystallized 1~3 time with glacial acetic acid, obtains double (3- the nitrobenzophenones) -6- hydroxyls of 2,3-
Base quinoxaline；
(2) by double (3- the nitrobenzophenones) -6- hydroxy quinoxalines of 2,3- and palladium carbon addition ethanol, mass concentration ratio is added
It is 80% hydrazine hydrate, wherein, the mass ratio of 2,3- double (3- nitrobenzophenones) -6- hydroxy quinoxalines and palladium carbon is 1:0.01~
0.04, hydrazine hydrate is 3.2~4 with the mol ratio of double (3- the nitrobenzophenones) -6- hydroxy quinoxalines of 2,3-:1, at a reflux temperature instead
5~10h is answered, is then filtered while hot, filtrate cooling room temperature separates out crystal, then through filtering, vacuum drying, obtain double (the 3- ammonia of 2,3-
Phenyl) -6- hydroxy quinoxalines；
(3) respectively by 2,3- double (3- aminophenyls) -6- hydroxy quinoxalines, substituted or non-substituted salicylide, sulfuric acid and ethanol
Be added in reaction vessel, wherein, 2,3- double (3- aminophenyls) -6- hydroxy quinoxalines and substituted or non-substituted salicylide mole
Than being 1:2,2,3- double (3- aminophenyls) -6- hydroxy quinoxalines and the mol ratio of sulfuric acid are 5:1, heating reflux reaction under agitation
6~10h, is subsequently cooled to room temperature, adds sodium borohydride, continues to stir 5~10min at room temperature, wherein, 2,3- double (3- ammonia
Phenyl) mol ratio of -6- hydroxy quinoxalines and sodium borohydride is 1:3~5, after reaction terminates, add water and dichloromethane, with distillation
Water washing organic phase for several times after, rotated evaporation removes dichloromethane, obtains double (3- (the substituted or non-substituted adjacent hydroxyl benzyls of 2,3-
Amido) phenyl) -6- hydroxy quinoxalines (abbreviation quinoxaline triphenol)；
(4) to addition quinoxaline triphenol, primary amine, paraformaldehyde and chloroform in reactor, wherein, quinoxaline triphenol,
The mol ratio of primary amine and paraformaldehyde is 1:1:4,16~24h of back flow reaction, are cooled to room temperature, then through 0.1~0.5mol/L's
Sodium hydroxide solution alkali cleaning, washing, the rotated evaporation of organic phase remove chloroform, and vacuum drying obtains single amine type of phenol-two not
Symmetrical three-functionality-degree quinoxalinyl benzoxazine monomer.
Preparation method of the invention can also include：
1st, described substituted or non-substituted bigcatkin willow aldehyde compound be Benzaldehyde,2-hydroxy, 4- methyl-Benzaldehyde,2-hydroxy,
5- methyl-Benzaldehyde,2-hydroxy, 4- methoxyl groups-Benzaldehyde,2-hydroxy, 5- methoxyl groups-Benzaldehyde,2-hydroxy, the fluoro- 2- hydroxy benzenes of 5-
One kind in the fluoro- Benzaldehyde,2-hydroxy of formaldehyde, 4-, 5- chlorine-2-hydroxyls benzaldehyde or the bromo- Benzaldehyde,2-hydroxies of 5-.
2nd, described fatty amine is C2~C12One kind in fatty amine, allyl amine, propargyl amine or chaff amine.
The invention provides a kind of with excellent fire resistance, heat resistance, wet-hot aging performance and excellent toughness
Asymmetric three-functionality-degree quinoxalinyl Polybenzoxazine resin, by adjusting rigidity and flexibility in fatty amine and phenolic compound
Group, to reduce the fusing point of benzoxazine monomer, improves the crosslink density and toughness of Polybenzoxazine, solves have larger space
The quinoxalinyl Polybenzoxazine molecular weight of steric hindrance structure is small, crosslink density is low, poor toughness and the introducing because of flexible group are led
The problem of pyrogenicity hydraulic performance decline, improves the processing characteristics of polymer, realizes that the structure and performance of Polybenzoxazine are controllable, expands benzene
Bing oxazine resin application fields.
The present invention by MOLECULE DESIGN, synthesized one it is similar when contain a hydroxyl and two amino quinoxaline molecule,
On this basis, oxazine ring is incorporated into quinoxaline molecular structure, obtains the asymmetric three-functionality-degree quinoline of amine type of a class list phenol-two
Quinoline base benzoxazine monomer, by regulating and controlling the quantity of aliphatic chain and aromatic rings, and assign such Polybenzoxazine have it is excellent
Hot property, mechanical property and good processing characteristics and toughness.
Asymmetric three-functionality-degree quinoxalinyl benzoxazine monomer structural characterization of the invention utilizes infrared spectrum
(Spotlight 100, PE companies of the U.S.) and nuclear magnetic resonance spectrometer (AVANCE-500, Switzerland Bruker), examination of infrared spectrum
Using pellet technique, Sample Scan 4 times, resolution ratio 4cm-1, sweep limits to 4000~500cm-1；Proton nmr spectra
It is that internal standard is made with tetramethylsilane (TMS), deuterated dimethyl sulfoxide (DMSO) makees solvent；Polymer performance test is using thermogravimetric point
Analyzer (TGA, TA companies of the U.S.) and dynamic thermomechanical analysis apparatus (DMA, TA companies of the U.S.).Wherein TGA uses nitrogen atmosphere, rises
Warm speed is 20 DEG C/min；DMA uses air atmosphere, single-cantilever pattern, and heating rate is 3 DEG C/min.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that, the embodiment of the present invention is only
It is used to further illustrate the present invention, but it is not intended that limiting the scope of the invention, the technology in the field is ripe
Practice personnel and some nonessential modifications and adaptations are made according to the content of the invention described above.
Embodiment 1
(1) to being separately added into m-dinitrobenzil (30.0g, 0.1mol) and 4- hydroxyl o-phenylenediamines in there-necked flask
(13.7g, 0.11mol) and 50mL glacial acetic acids, mixture back flow reaction 5h, after being subsequently cooled to room temperature, are collected by filtration what is formed
Precipitation, drying, gained crude product is recrystallized 2 times with glacial acetic acid, obtains double (3- the nitrobenzophenones) -6- hydroxy quinoxaline crystal of 2,3-
(31.6g), yield 81.5%；
(2) by double (3- the nitrobenzophenones) -6- hydroxy quinoxalines (19.4g, 0.05mol) of 2,3- and palladium-carbon catalyst (0.4g)
It is added in 300mL ethanol, is then added dropwise over 80% hydrazine hydrate (8.8g, 0.176mol), 8h is reacted at a reflux temperature, takes advantage of
Heat filtering, removes palladium-carbon catalyst, and filtrate is cooled to room temperature, separates out crystal, filtering, then washes 3~4 times with distilled water, finally
It is vacuum dried, obtain double (3- the aminophenyls) -6- hydroxy quinoxalines (14.9g) of 2,3-, yield 90.8%；
(3) by double (3- the aminophenyls) -6- hydroxy quinoxalines (16.4g, 0.05mol) of 2,3-, Benzaldehyde,2-hydroxy (12.2g,
0.10mol), the concentrated sulfuric acid (1.0g, 0.01mol) and 100mL ethanol be added to equipped with agitator, condenser pipe, three mouthfuls of thermometer
In flask, 8h is heated to reflux, reaction is cooled to room temperature after terminating, add sodium borohydride (7.9g, 0.21mol), continues at room temperature
Stirring 6min, is subsequently adding distilled water, is extracted with dichloromethane, repeatedly washing, is finally separating out organic phase, and rotary evaporation is removed
Solvent, obtains double (3- (2- hydroxyls-benzamido group) the phenyl) -6- hydroxy quinoxalines (22.6g), yield 83.4% of 2,3-；
(4) to added in reactor double (3- (2- hydroxyls-benzamido group) the phenyl) -6- hydroxy quinoxalines of 2,3- (10.8g,
0.02mol), n-butylamine (1.43g, 0.02mol), paraformaldehyde (2.4g, 0.08mol) and 50mL chloroforms, back flow reaction
Terminate after 20h, be cooled to room temperature, with the NaOH solution alkali cleaning of 0.3mol, then with water washing is distilled 3~5 times, be then demultiplex out
Machine phase, rotary evaporation removes chloroform, and vacuum drying finally obtains the butylamine-mono- amine type of phenol-two three-functionality-degree quinoxalinyl benzene
Bing oxazines monomer (10.7g), yield is 80.8%, and fusing point is 93.6 DEG C.
Proton nmr spectra test result (500M, DMSO, ppm)：8.30~6.62 (m, 18H, Ar-H), 5.25 (s, 2H,
O-CH2- N), 5.22 (s, 2H, O-CH2- N), 5.01 (s, 2H, O-CH2- N), 4.38 (s, 2H, Ar-CH2- N), 4.36 (s, 2H,
Ar-CH2- N), 3.94 (s, 2H, Ar-CH2- N), 2.70 (t, 2H, N-CH2-CH2), 1.51 (m, 2H, CH2-CH2-CH2), 1.34
(m, 2H, CH2-CH2-CH2), 0.91 (t, 3H ,-CH3)；Examination of infrared spectrum result (KBr, cm-1)：1608 and 1510 (phenyl ring bones
Frame vibrates), 1341 and 1322 (CH in the oxazine rings that are respectively connected with phenyl ring and quinoxaline ring2Rocking vibration), 1235 Hes
1069 (respectively C-O-C asymmetric and symmetrical stretching vibration), 1162 (C-N-C asymmetric stretching vibrations), 933~951 (respectively
It is c h bond out-of-plane bending vibration in the oxazine ring being connected with quinoxaline ring and phenyl ring, is also the feature with oxazine ring on phenyl ring
Absworption peak), 746,810 and 721 (respectively phenyl ring ortho positions and the dibasic characteristic peak of meta), with reference to proton nmr spectra and red
External spectrum confirms to contain San oxazine ring in products therefrom, is target product.
The benzoxazine monomer of gained is put into electric drying oven with forced convection, thermosetting is carried out to monomer using programmed temperature method
Change, curing cycle is：180 DEG C/2h, 200 DEG C/2h, 220 DEG C/3h, 240 DEG C/2h, obtain Polybenzoxazine resin, through DMA and
TGA is tested, and the glass transition temperature for obtaining Polybenzoxazine resin (is abbreviated as Tg) for 353 DEG C, it is weightless 5% and 10% right
The heat decomposition temperature answered (is abbreviated as T5And T10) 382 and 405 DEG C are respectively, the carbon yield at 800 DEG C (is abbreviated as Yc) be up to
57.3%.
Embodiment 2
Except raw material Benzaldehyde,2-hydroxy is changed to 4- methyl-Benzaldehyde,2-hydroxy (13.6g, 0.10mol) in step (3), step
Suddenly double (3- (2- hydroxyls-benzamido group) the phenyl) -6- hydroxy quinoxalines of 2,3- in (4) are changed to double (3- (the 2- hydroxy-5-methyls of 2,3-
Base-benzamido group) phenyl) -6- hydroxy quinoxalines (11.4g, 0.02mol) outward, other conditions are finally obtained containing first with embodiment 1
The butylamine of the base-mono- amine type of phenol-two three-functionality-degree quinoxalinyl benzoxazine monomer (11.2g), yield 81.3%, fusing point is 109
℃。
Proton nmr spectra test result (500M, DMSO, ppm)：8.27~6.65 (m, 16H, Ar-H), 5.20 (s, 2H,
O-CH2- N), 5.17 (s, 2H, O-CH2- N), 5.03 (s, 2H, O-CH2- N), 4.34 (s, 2H, Ar-CH2- N), 4.31 (s, 2H,
Ar-CH2- N), 3.90 (s, 2H, Ar-CH2- N), 2.71 (t, 2H, N-CH2-CH2), 2.20 (s, 6H ,-CH3), 1.50 (m, 2H,
CH2-CH2-CH2), 1.35 (m, 2H, CH2-CH2-CH2), 0.90 (t, 3H ,-CH3)；Examination of infrared spectrum result (KBr, cm-1)：
1611st, 1508,1345,1323,1233,1067,1158,932~949,810 and 721,861 (phenyl ring 1,2, the trisubstituted spies of 4-
Levy peak), confirm to contain three oxazine rings in products therefrom with reference to proton nmr spectra and infrared spectrum, it is target product.
Solidification and test condition are with embodiment 1, the T of Polybenzoxazine resing、T5、T10And YcRespectively 336 DEG C of value, 375
DEG C, 396 DEG C and 55.7%.
Embodiment 3
Except raw material Benzaldehyde,2-hydroxy is changed to 5- methoxyl groups-Benzaldehyde,2-hydroxy (15.2g, 0.10mol) in step (3),
Double (3- (2- hydroxyls-benzamido group) phenyl) -6- hydroxy quinoxalines of 2,3- in step (4) are changed to the double (3- (2- hydroxyls -4- of 2,3-
Methoxy-benzylamine base) phenyl) -6- hydroxy quinoxalines (12.0g, 0.02mol), n-butylamine be changed to n-octyl amine (2.58g,
0.02mol) outward, other conditions finally obtain the octylame containing the methoxyl group-mono- amine type of phenol-two three-functionality-degree quinoxaline with embodiment 1
Base benzoxazine monomer (11.8g), yield 75.8%, fusing point is 73 DEG C.
Proton nmr spectra test result (500M, DMSO, ppm)：8.27~6.65 (m, 16H, Ar-H), 5.20 (s, 2H,
O-CH2- N), 5.17 (s, 2H, O-CH2- N), 5.03 (s, 2H, O-CH2- N), 4.34 (s, 2H, Ar-CH2- N), 4.31 (s, 2H,
Ar-CH2- N), 3.95 (s, 3H ,-OCH3), 3.88 (s, 2H, Ar-CH2- N), 2.74 (t, 2H, N-CH2-CH2), 1.54~1.26
(m, 12H, CH2-CH2-CH2), 0.87 (t, 3H ,-CH3)；Examination of infrared spectrum result (KBr, cm-1)：1611、1505、1365、
1320th, 1228,1066,1163,937~952,812,735,860, confirm that gained is produced with reference to proton nmr spectra and infrared spectrum
Contain San oxazine ring in thing, be target product.
Solidification and test condition are with embodiment 1, the T of Polybenzoxazine resing、T5、T10And YcRespectively 316 DEG C of value, 364
DEG C, 389 DEG C and 49.5%.
Embodiment 4
Except raw material Benzaldehyde,2-hydroxy is changed to the fluoro- Benzaldehyde,2-hydroxies of 5- (14.1g, 0.10mol), step in step (3)
(4) double (3- (2- hydroxyls-benzamido group) the phenyl) -6- hydroxy quinoxalines of 2,3- in are changed to double (3- (the 2- hydroxyl-5-fluorines-benzyl of 2,3-
Amido) phenyl) -6- hydroxy quinoxalines (11.5g, 0.02mol), n-butylamine is changed to chaff amine (1.94g, 0.02mol) outward, other
Part finally obtains the fluorine-containing chaff amine-mono- amine type of phenol-two three-functionality-degree quinoxalinyl benzoxazine monomer with embodiment 1
(10.8g), yield 74.8%, fusing point is 102 DEG C.
Proton nmr spectra test result (500M, DMSO, ppm)：8.44~6.62 (m, 16H, Ar-H), 7.44 (s, 1H,
Furan nucleus-CH=CH-O-), 6.23~6.38 (s, 2H, furan nucleus=CH-CH=), 5.38 (s, 2H, O-CH2- N), 5.34 (s,
2H, O-CH2- N), 4.89 (s, 2H, furan nucleus O-CH2- N), 4.55 (s, 2H, Ar-CH2- N), 4.48 (s, 2H, Ar-CH2- N),
4.02 (s, 2H, the Ar-CH being connected with furan nucleus2- N), 3.95 (s, 2H, N-CH2-)；Examination of infrared spectrum result (KBr, cm-1)：1613rd, 1505,1365,1323,1230,1028,1066,1165,925~952,810,721 and 866,1572,973 and
765 (characteristic peaks of furan nucleus), confirm to contain three oxazine rings in products therefrom with reference to proton nmr spectra and infrared spectrum, are
Target product.
In addition to solidify afterwards temperature increased 260 DEG C/2h, early stage curing cycle and test condition finally give with embodiment 1
Polybenzoxazine resin Tg、T5、T10And YcValue is respectively 388 DEG C, 425 DEG C, 453 DEG C and 68.7%.
Embodiment 5
Except the n-butylamine in step (4) is changed to allylamine (1.14g, 0.02mol) outward, other conditions with embodiment 1, finally
Obtain the allylamine-mono- amine type of phenol-two three-functionality-degree quinoxalinyl benzoxazine monomer (9.8g), yield 75.9%, fusing point 108
℃。
Proton nmr spectra test result (500M, DMSO, ppm)：8.32~6.61 (m, 18H, Ar-H), 5.85 (m, 1H,
In pi-allyl=CH-), 5.18 (m, 2H, in pi-allyl=CH2), 5.24 (s, 2H, O-CH2- N), 5.20 (s, 2H, O-CH2- N),
5.01 (s, 2H, O-CH2- N), 4.55 (s, 2H, Ar-CH2- N), 4.48 (s, 2H, Ar-CH2- N), 3.98 (s, 2H, Ar-CH2-
N), 3.34 (s, 2H, N-CH2-)；Examination of infrared spectrum result (KBr, cm-1)：1642 (C=C stretching vibrations), 1612,1504,
1370th, 1324,1233,1068,1172,990 (=C-H is waved outside face), 928~950,811,744 and 718, it is common with reference to nuclear-magnetism
To shake confirmed with infrared spectrum and contain San oxazine ring in products therefrom, be target product.
Curing cycle and test condition with embodiment 4, the T of the Polybenzoxazine resin for finally givingg、T5、T10And YcValue point
Wei 371 DEG C, 402 DEG C, 434 DEG C and 63.6%.
The excellent heat resistance that the present invention is had in itself by means of quinoxaline molecule, draws by quinoxaline molecular structure
Enter the oxazine ring of not same type, obtain the new single amine type of phenol-two three-functionality-degree quinoxalinyl benzoxazine monomer of a class, pass through
Introduce flexible alkyl chain and polymerizable groups so that such monomer has relatively low fusing point and extra polymerization crosslinking position, from
And improve processing characteristics, and the introducing of Geng Duo oxazine rings is added, the Polybenzoxazine resin that thus prepared by monomer shows excellent
Heat resistance and good mechanical property, can be used to manufacturing high performance structures materials, electronic package material, high-temperature Resistance Adhesives,
Ablation resistant material, resistant material etc., are with a wide range of applications in fields such as electronics, Aero-Space, machine-building.
Claims (4)
1. a kind of asymmetric three-functionality-degree quinoxalinyl benzoxazine of single amine type of phenol-two has following structure：
In formula, R1It is H, CH3Or OCH3In one kind, R2It is C2~C12Alkyl, pi-allyl, propargyl or fural in
It is a kind of.
2. the preparation method of the asymmetric three-functionality-degree quinoxalinyl benzoxazine of single amine type of phenol-two described in a kind of claim 1,
It is characterized in that：
(1) to addition m-dinitrobenzil, 4- hydroxyls o-phenylenediamine and glacial acetic acid in container, wherein, m-dinitrobenzil
It is 1 with the mol ratio of 4- hydroxyl o-phenylenediamines:1~1.2, mixture reacts 4~8h at a reflux temperature, is subsequently cooled to room
Temperature, filtering, filter cake drying, gained crude product is recrystallized 1~3 time with glacial acetic acid, obtains double (3- the nitrobenzophenones) -6- hydroxyls of 2,3-
Quinoxaline；
(2) by double (3- the nitrobenzophenones) -6- hydroxy quinoxalines of 2,3- and palladium carbon addition ethanol, adding mass concentration ratio is
80% hydrazine hydrate, wherein, the mass ratio of 2,3- double (3- nitrobenzophenones) -6- hydroxy quinoxalines and palladium carbon is 1:0.01~0.04,
Hydrazine hydrate is 3.2~4 with the mol ratio of double (3- the nitrobenzophenones) -6- hydroxy quinoxalines of 2,3-:1, at a reflux temperature react 5~
10h, then filters while hot, filtrate cooling room temperature, separates out crystal, then through filtering, vacuum drying, obtains double (the 3- phenalgins of 2,3-
Base) -6- hydroxy quinoxalines；
(3) double (3- the aminophenyls) -6- hydroxy quinoxalines of 2,3-, substituted or non-substituted salicylide, sulfuric acid and ethanol are added respectively
To in reaction vessel, wherein, 2,3- double (3- aminophenyls) -6- hydroxy quinoxalines are with the mol ratio of substituted or non-substituted salicylide
1:2,2,3- double (3- aminophenyls) -6- hydroxy quinoxalines and the mol ratio of sulfuric acid are 5:1, under agitation heating reflux reaction 6~
10h, is subsequently cooled to room temperature, adds sodium borohydride, continues to stir 5~10min at room temperature, wherein, 2,3- double (3- phenalgins
Base) mol ratio of -6- hydroxy quinoxalines and sodium borohydride is 1:3~5, after reaction terminates, add water and dichloromethane, use distilled water
After washing organic phase for several times, rotated evaporation removes dichloromethane, obtains double (3- (the substituted or non-substituted adjacent hydroxy benzylamines of 2,3-
Base) phenyl) -6- hydroxy quinoxalines (abbreviation quinoxaline triphenol)；
(4) to addition quinoxaline triphenol, primary amine, paraformaldehyde and chloroform in reactor, wherein, quinoxaline triphenol, primary amine
It is 1 with the mol ratio of paraformaldehyde:1:4,16~24h of back flow reaction, are cooled to room temperature, then through the hydrogen-oxygen of 0.1~0.5mol/L
Change sodium solution alkali cleaning, washing, the rotated evaporation of organic phase removes chloroform, and vacuum drying obtains single amine type of phenol-two asymmetric
Three-functionality-degree quinoxalinyl benzoxazine monomer.
3. the preparation method of the asymmetric three-functionality-degree quinoxalinyl benzoxazine of single amine type of phenol-two according to claim 2,
It is characterized in that：Described substituted or non-substituted bigcatkin willow aldehyde compound be Benzaldehyde,2-hydroxy, 4- methyl-Benzaldehyde,2-hydroxy,
One kind in 5- methyl-Benzaldehyde,2-hydroxy, 4- methoxyl groups-Benzaldehyde,2-hydroxy or 5- methoxyl groups-Benzaldehyde,2-hydroxy.
4. the preparation side of the asymmetric three-functionality-degree quinoxalinyl benzoxazine of single amine type of phenol-two according to Claims 2 or 3
Method, it is characterized in that：Described primary amine is C2~C12One kind in fatty amine, allyl amine, propargyl amine or chaff amine.
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