CN105061466A - Main chain bisphenol type quinoxaline benzoxazine and preparation method thereof - Google Patents
Main chain bisphenol type quinoxaline benzoxazine and preparation method thereof Download PDFInfo
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- CN105061466A CN105061466A CN201510551817.2A CN201510551817A CN105061466A CN 105061466 A CN105061466 A CN 105061466A CN 201510551817 A CN201510551817 A CN 201510551817A CN 105061466 A CN105061466 A CN 105061466A
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- amine
- quinoxaline
- main chain
- bisphenol type
- benzoxazine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
Abstract
The invention relates to main chain bisphenol type quinoxaline benzoxazine and a preparation method thereof. The method comprises the steps that a main chain type quinoxaline bisphenol mixture is synthesized by taking 4- hydroxyl benzil and 4-hydroxyl o-phenylenediamine as the raw materials, and a bisphenol type quinoxaline benzoxazine mixed monomer with a quinoxaline ring located in a main chain is prepared by performing a Mannich condensation reaction on the mixture and primary amine; by changing an amine source and regulating the composition and proportion of mixed amine, the fusion temperature of the monomer can be lowered, and the processing performance can be improved; through regulation and control of flexible groups, rigid groups and polymerizable groups and the existence of more intramolecular and intermolecular hydrogen bonds, main chain bisphenol type quinoxaline polybenzoxazine resin has the better thermostability, flame retardant property, damp-heat resistance property and mechanical property and can be used for manufacturing high-property structure materials, electronic packaging materials, corrosion-resistant materials, flame retardant materials and the like.
Description
Technical field
What the present invention relates to is a kind of organic polymer material, the present invention also relates to a kind of preparation method of organic polymer material.Specifically a kind of main chain bisphenol type quinoxalinyl benzoxazine and preparation method thereof.
Background technology
Benzoxazine colophony is a kind of novel phenolic resins received much concern in recent years, it is on the basis inheriting traditional resol kind excellent properties, no longer must have when also there is solidification in acid catalysis, solidification and also occur volumetric shrinkage hardly, namely volume zero shrinks, also can not discharge the features such as small molecules, and handiness is higher in molecular designing, simultaneously it has the excellent specific properties such as autocatalytic polymerization ability and high temperature resistant, good flame retardation effect of being heated.These advantages make benzoxazine colophony obtain tremendous development in the field such as electronic package material, aerospace material.
Quinoxaline is a kind of heterogeneous ring compound, it is condensed by a phenyl ring and a pyrazine ring and forms, 2, various active group can be introduced for 3,6, there is molecular designing very flexibly, can be used for the polymkeric substance such as synthesis polyphenylene quinoxaline, quinoxalinyl polyimide, polyethers, polyester.Meanwhile, this quinoxaline structure has higher bond energy, huge molecular volume and more weak polarity, imparts with the excellent heat-resisting and thermo-oxidative stability of its obtained polymkeric substance, resistance to environmental stability, low-k and dielectric loss, in organic solvent good solubility and good Mechanical Processability.
Summary of the invention
The object of the present invention is to provide a kind of main chain bisphenol type quinoxalinyl benzoxazine with excellent thermal characteristics and mechanical property.The present invention also aims to the preparation method that a kind of main chain bisphenol type quinoxalinyl benzoxazine is provided.
The object of the present invention is achieved like this:
The structural formula of main chain bisphenol type quinoxalinyl benzoxazine monomer is:
In formula, R is C
2~ C
10one in alkyl, phenyl, o-tolyl, a tolyl, adjacent ethylphenyl, an ethylphenyl, m-methoxyphenyl or furfurylidene.
Main chain bisphenol type quinoxalinyl benzoxazine monomer of the present invention is prepared in such a way:
(1) using glacial acetic acid as solvent, 4-hydroxyl benzil and 4-hydroxyl O-Phenylene Diamine that mol ratio is 1:1 ~ 1.2 is added in container, mixture backflow 6 ~ 12h, after being cooled to room temperature, throw out glacial acetic acid recrystallization, obtains 2-(4-hydroxyphenyl)-3-phenyl-6-hydroxy quinoxaline and 2-phenyl-3-(4-hydroxyphenyl)-6-hydroxy quinoxaline mixture, is abbreviated as quinoxaline bis-phenol;
(2) quinoxaline bis-phenol, primary amine, paraformaldehyde and toluene or dimethylbenzene are joined in container successively, the mol ratio of quinoxaline bis-phenol, primary amine and paraformaldehyde is 1:2:4,4 ~ 8h is reacted at 90 ~ 160 DEG C, n-hexane is added after reaction terminates, again after filtration, n-hexane, drying, obtain main chain bisphenol type quinoxalinyl benzoxazine monomer.
Primary amine described in step (2) is C
2~ C
10aliphatic amide, aniline, Ortho Toluidine, meta-aminotoluene, o ethyl aniline, m-ethyl aniline, m-anisidine, chaff amine or by C
2~ C
10one in the mixed amine that saturated fatty amine and other amine form, C in mixed amine
2~ C
10the mol ratio of saturated fatty amine and other amine is 1:0.2 ~ 2.
Main chain bisphenol type quinoxalinyl benzoxazine monomer structural characterization of the present invention utilizes infrared spectra (Spotlight100, PE company of the U.S.) and nuclear magnetic resonance spectrometer (AVANCE-500, Switzerland Bruker), examination of infrared spectrum adopts pellet technique, Sample Scan 4 times, resolving power 4cm
-1, sweep limit is to 4000 ~ 500cm
-1, proton nmr spectra is mark in doing with tetramethylsilane (TMS), and deuterated dimethyl sulfoxide (DMSO) makes solvent.Polymer performance test adopts thermogravimetric analyzer (TGA, TA company of the U.S.) and differential scanning calorimeter (DSC, TA company of the U.S.).Wherein TGA and DSC all uses nitrogen atmosphere, and temperature rise rate is 20 DEG C/min.
The present invention is from the angle of molecular designing, to utilize in quinoxaline 2, 3, 6 have higher activity, synthesize a kind of quinoxaline bis-phenol, due to the molecular structure that quinoxaline is special, this quinoxaline bis-phenol is the different tautomer of a kind of space structure, as shown in Figure 1, namely the mixture of two kinds of molecular structure: 2-(4-hydroxyphenyl)-3-phenyl-5-hydroxy quinoxalines and 2-phenyl-3-(4-hydroxyphenyl)-5-hydroxy quinoxaline is contained, for Material synthesis goes out a class, there is different spaces configuration with it, and quinoxaline ring is positioned at the diamine type quinoxalinyl benzoxazine mixture of main chain.
The present invention to relate to 4-hydroxyl benzil and 4-hydroxyl O-Phenylene Diamine as raw material, has synthesized backbone chain type quinoxaline bisphenol mixture, then by with C
2~ C
10aliphatic amide, aniline, Ortho Toluidine, meta-aminotoluene, o ethyl aniline, m-ethyl aniline, m-anisidine, chaff amine or by C
2~ C
10the mixed amine that saturated fatty amine and other amine form carries out Mannich condensation reaction, thus has prepared the bisphenol type quinoxalinyl benzoxazine mix monomer that quinoxaline ring is positioned at main chain; By changing composition and the ratio of amine source and adjustment mixed amine, the melt temperature of monomer can be reduced, improve processing characteristics, by the regulation and control of flexible group, rigid radical and polymerizable groups, add in more molecule and the existence of intermolecular hydrogen bonding, make main chain bisphenol type quinoxalinyl Polybenzoxazine resin have more excellent thermostability, flame retardant properties, wet-hot aging performance and mechanical property, can be used for manufacturing high performance structures material, electronic package material, corrosion resistant material and fire retardant material etc.
Accompanying drawing explanation
Fig. 1 is the structural formula of main chain bisphenol type quinoxalinyl benzoxazine monomer of the present invention.
Fig. 2 is the different tautomer schematic diagram of quinoxaline bis-phenol space structure.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is; the embodiment of the present invention is only used to further illustrate the present invention; but can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field makes some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
(1) in there-necked flask, add 4-hydroxyl benzil (22.6g, 0.1mol) with 4-hydroxyl O-Phenylene Diamine (12.4g, 0.1mol) with 250mL glacial acetic acid, mixture backflow 10h, after being cooled to room temperature, filter, collect the precipitation formed, dry, crude product glacial acetic acid recrystallization, obtain 2-(4-hydroxyphenyl)-3-phenyl-6-hydroxy quinoxaline and 2-phenyl-3-(4-hydroxyphenyl)-6-hydroxy quinoxaline mixture (quinoxaline bis-phenol) of 28.4g, yield 90.4%;
(2) by quinoxaline bis-phenol (15.7g, 0.05mol), aniline (9.3g, 0.1mol), paraformaldehyde (6.0g, 0.2mol) join in there-necked flask with 20mL dimethylbenzene, at 140 DEG C of temperature, react 6h, products therefrom is added in normal hexane, and with n-hexane for several times, vacuum-drying, finally obtains aniline-bisphenol type quinoxalinyl benzoxazine monomer, yield 77.8%.
Proton nmr spectra test result (500M, DMSO, ppm): 8.32 ~ 6.51 (m, 20H, Ar-H), 5.42 (s, 2H, O-CH
2-N), 5.26 (s, 2H, O-CH
2-N), 4.43 (s, 2H, Ar-CH
2-N), 4.24 (s, 2H, Ar-CH
2-N); Examination of infrared spectrum result (KBr, cm
-1): CH on 1321 (oxazine rings
2rocking vibration), 1232 and 1069 (C-O-C asymmetric and symmetrical stretching vibration), 1175 (the upper asymmetrical stretching vibrations of C-N-C), 942 and 951 (c h bond out-of-plane deformation vibrations, also be the charateristic avsorption band of phenyl ring Dai You oxazine ring), confirmation products therefrom is subject monomers.
The benzoxazine monomer of gained is put into electric drying oven with forced convection, and adopt programmed temperature method to carry out thermofixation to monomer, curing cycle is: 180 DEG C/2h, 200 DEG C/2h, 220 DEG C/2h, 240 DEG C/2h, obtains Polybenzoxazine resin.Through DSC and TGA test, the second-order transition temperature obtaining Polybenzoxazine resin (is abbreviated as T
g) heat decomposition temperature corresponding to 236 DEG C, weightless 5% and 10% (is abbreviated as T
5and T
10) being respectively 350 and 383 DEG C, the carbon yield at 800 DEG C (is abbreviated as Y
c) 52.5%.
Embodiment 2
Except 4-hydroxyl O-Phenylene Diamine consumption in step (1) changes 13.6g into, reflux time changes 8h into, aniline in step (2) changes n-Butyl Amine 99 (7.3g) into, dimethylbenzene changes toluene into, temperature of reaction changes into outside 110 DEG C, other conditions, with embodiment 1, finally obtain n-Butyl Amine 99-bisphenol type quinoxalinyl benzoxazine monomer, yield 82.3%.
Proton nmr spectra test result (500M, DMSO, ppm): 8.34 ~ 6.60 (m, 10H, Ar-H), 4.95 (s, 2H, O-CH
2-N), 4.86 (s, 2H, O-CH
2-N), 3.93 (s, 2H, Ar-CH
2-N), 3.85 (s, 2H, Ar-CH
2-N), 2.72 (t, 2H, N-CH
2-CH
2), 2.62 (t, 4H, N-CH
2-CH
2), 1.35 ~ 1.52 (m, 8H, CH
2-CH
2-CH
2), 0.88 (t, 3H ,-CH
3); Examination of infrared spectrum result (KBr, cm
-1): 2955,2930 and 2858 (methyl and methylene radical C-H stretching vibrations), 1325,1232,1072,1175,941 and 949.
Solidification and test condition with embodiment 1, the T of Polybenzoxazine resin
g, T
5, T
10and Y
cvalue is respectively 195 DEG C, 337 DEG C, 359 DEG C and 41.3%.
Embodiment 3
Except the n-Butyl Amine 99 in step (2) changes n-octyl amine (12.9g) into, other conditions, with embodiment 2, finally obtain n-octyl amine-bisphenol type quinoxalinyl benzoxazine monomer, yield 77.5%.
Proton nmr spectra test result (500M, DMSO, ppm): 8.33 ~ 6.58 (m, 10H, Ar-H), 4.98 (s, 2H, O-CH
2-N), 4.86 (s, 2H, O-CH
2-N), 3.91 (s, 2H, Ar-CH
2-N), 3.83 (s, 2H, Ar-CH
2-N), 2.73 (t, 2H, N-CH
2-CH
2), 2.60 (t, 2H, N-CH
2-CH
2), 1.28 ~ 1.57 (m, 24H, CH
2-CH
2-CH
2), 0.86 (t, 6H ,-CH
3); Examination of infrared spectrum result (KBr, cm
-1): 2953,2931,2862,1324,1232,1071,1166,940 and 949.
Solidification and test condition with embodiment 1, the T of Polybenzoxazine resin
g, T
5, T
10and Y
cvalue is respectively 171 DEG C, 333 DEG C, 355 DEG C and 30.1%.
Embodiment 4
Except aniline in step (2) changes into except chaff amine (9.7g), other conditions, with embodiment 1, finally obtain chaff amine-bisphenol type quinoxalinyl benzoxazine monomer, yield 72.7%.
Proton nmr spectra test result (500M, DMSO, ppm): 8.43 ~ 6.65 (m, 10H, Ar-H), 7.41 (s, 2H ,-CH=CH-O-), 6.25 ~ 6.37 (s, 4H,=CH-CH=), 4.95 (s, 2H, O-CH
2-N), 4.86 (s, 2H, O-CH
2-N), 4.05 (s, 2H, Ar-CH
2-N), 4.03 (s, 2H, Ar-CH
2-N), 3.94 (s, 4H, N-CH
2-); Examination of infrared spectrum result (KBr, cm
-1): 1323,1234,1065,1164,940,946,1570,975 and 760 (characteristic peak of furan nucleus).
Except after fixing temperature adds 260 DEG C/2h, curing cycle and test condition are with embodiment 1 in earlier stage, the T of the Polybenzoxazine resin finally obtained
g, T
5, T
10and Y
cvalue is respectively 286 DEG C, 395 DEG C, 438 DEG C and 59.1%.
Embodiment 5
Except n-Butyl Amine 99 in step (2) changes the mixture of n-octyl amine and aniline into, n-octyl amine and aniline add-on are respectively outside 6.5g and 4.6g, and other conditions, with embodiment 2, finally obtain mixed amine-bisphenol type quinoxalinyl benzoxazine monomer, yield 80.1%.
Proton nmr spectra test result (500M, DMSO, ppm): 8.33 ~ 6.65 (m, Ar-H), 5.40 and 5.23 (s, O-CH
2-N), 4.98 and 4.86 (s, O-CH
2-N), 4.45 and 4.23 (s, Ar-CH
2-N), 3.91 and 3.82 (s, Ar-CH
2-N), 2.70 and 2.61 (t, N-CH
2-CH
2), 1.52 ~ 1.22 (m, CH
2-CH
2-CH
2), 0.90 (t ,-CH
3); Examination of infrared spectrum result (KBr, cm
-1): 2952,2930,2847,1322,1233,1070,1166,934 and 949.
Solidification and test condition with embodiment 1, the T of Polybenzoxazine resin
g, T
5, T
10and Y
cvalue is respectively 215 DEG C, 352 DEG C, 375 DEG C and 47.5%.
Embodiment 6
Except n-octyl amine in step (2) and aniline change n-Butyl Amine 99 and meta-aminotoluene into, add-on changes into outside 4.4g and 4.3g respectively, and other conditions, with embodiment 5, finally obtain mixed amine-bisphenol type quinoxalinyl benzoxazine monomer, yield 72.6%.
Proton nmr spectra test result (500M, DMSO, ppm): 8.37 ~ 6.62 (m, Ar-H), 5.37 and 5.21 (s, O-CH
2-N), 4.91 and 4.82 (s, O-CH
2-N), 4.44 and 4.25 (s, Ar-CH
2-N), 3.90 and 3.84 (s, Ar-CH
2-N), 2.60 ~ 2.73 (t, N-CH
2-CH
2), 2.28 (s, Ar-CH
3), 1.34 ~ 1.54 (m, CH
2-CH
2-CH
2), 0.89 (t ,-CH
3); Examination of infrared spectrum result (KBr, cm
-1): 2950,2934,2848,1325,1232,1066,1173,932 and 950.
Solidification and test condition with embodiment 1, the T of Polybenzoxazine resin
g, T
5, T
10and Y
cvalue is respectively 218 DEG C, 349 DEG C, 372 DEG C and 46.3%.
Embodiment 7
Except n-octyl amine in step (2) and aniline change n-Butyl Amine 99 and chaff amine into, add-on changes into outside 3.6g and 4.3g respectively, and other conditions, with embodiment 5, finally obtain mixed amine-bisphenol type quinoxalinyl benzoxazine monomer, yield 72.6%.
Proton nmr spectra test result (500M, DMSO, ppm): 8.41 ~ 6.63 (m, Ar-H), 7.40 (s ,-CH=CH-O-), 6.26 ~ 6.38 (s ,=CH-CH=), 4.85 ~ 4.94 (s, O-CH
2-N), 4.02 ~ 4.05 (s, Ar-CH
2-N), 3.83 ~ 3.95 (s, Ar-CH
2-N and N-CH
2-), 2.63 ~ 2.70 (t, N-CH
2-CH
2), 1.36 ~ 1.53 (m, CH
2-CH
2-CH
2), 0.90 (t ,-CH
3); Examination of infrared spectrum result (KBr, cm
-1): 2954,2932,2853,1322,1235,1065,1174,941,948,1571,978 and 759.
Solidification and test condition with embodiment 4, the T of Polybenzoxazine resin
g, T
5, T
10and Y
cvalue is respectively 243 DEG C, 379 DEG C, 402 DEG C and 50.4%.
As can be seen from the above-described embodiment, the present invention to utilize in quinoxaline 2,3,6 to have higher activity, synthesize a kind of main chain bisphenol type quinoxalinyl benzoxazine mix monomer, because quinoxaline ring is positioned among main polymer chain, the sterie configuration of mix monomer molecule is different, the sterically hindered reduction of polymer segment, the free volume of polymer network declines, and the accumulation of polymer segment is finer and close; And by changing amine source and adjusting composition and the ratio of mixed amine, the melt temperature of monomer can be reduced, improve processing characteristics, by the regulation and control of flexible group, rigid radical and polymerizable groups, add in more molecule and the existence of intermolecular hydrogen bonding, make main chain bisphenol type quinoxalinyl Polybenzoxazine resin have more excellent thermostability, flame retardant properties, wet-hot aging performance and mechanical property, can be used for manufacturing high performance structures material, electronic package material, corrosion resistant material and fire retardant material etc.
Claims (3)
1. a main chain bisphenol type quinoxalinyl benzoxazine, is characterized in that the structural formula of monomer is:
In formula, R is C
2~ C
10one in alkyl, phenyl, o-tolyl, a tolyl, adjacent ethylphenyl, an ethylphenyl, m-methoxyphenyl or furfurylidene.
2. a preparation method for main chain bisphenol type quinoxalinyl benzoxazine according to claim 1, is characterized in that comprising the steps:
(1) using glacial acetic acid as solvent, 4-hydroxyl benzil and 4-hydroxyl O-Phenylene Diamine that mol ratio is 1:1 ~ 1.2 is added in container, mixture backflow 6 ~ 12h, after being cooled to room temperature, throw out glacial acetic acid recrystallization, obtains 2-(4-hydroxyphenyl)-3-phenyl-6-hydroxy quinoxaline and 2-phenyl-3-(4-hydroxyphenyl)-6-hydroxy quinoxaline mixture, is abbreviated as quinoxaline bis-phenol;
(2) quinoxaline bis-phenol, primary amine, paraformaldehyde and toluene or dimethylbenzene are joined in container successively, the mol ratio of quinoxaline bis-phenol, primary amine and paraformaldehyde is 1:2:4,4 ~ 8h is reacted at 90 ~ 160 DEG C, n-hexane is added after reaction terminates, again after filtration, n-hexane, drying, obtain main chain bisphenol type quinoxalinyl benzoxazine monomer.
3. the preparation method of main chain bisphenol type quinoxalinyl benzoxazine according to claim 2, is characterized in that: described primary amine is C
2~ C
10aliphatic amide, aniline, Ortho Toluidine, meta-aminotoluene, o ethyl aniline, m-ethyl aniline, m-anisidine, chaff amine or by C
2~ C
10one in the mixed amine that saturated fatty amine and other amine form, C in mixed amine
2~ C
10the mol ratio of saturated fatty amine and other amine is 1:0.2 ~ 2.
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Cited By (1)
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