CN103288680B - Self-catalyzed fluorenyl bisphthalonitrile resin monomer and preparation method thereof - Google Patents
Self-catalyzed fluorenyl bisphthalonitrile resin monomer and preparation method thereof Download PDFInfo
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- CN103288680B CN103288680B CN201310168538.9A CN201310168538A CN103288680B CN 103288680 B CN103288680 B CN 103288680B CN 201310168538 A CN201310168538 A CN 201310168538A CN 103288680 B CN103288680 B CN 103288680B
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- fluorenes
- aminophenyl
- dihydroxyl
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Abstract
The invention provides a self-catalyzed fluorenyl bisphthalonitrile resin monomer and a preparation method thereof. The preparation method comprises the following steps of: adding bisphenol-bisamidofluorene, 4-nitrophthalonitrile, anhydrous potassium carbonate and organic solvents into a reaction vessel, wherein the molar ratio of the bisphenol-bisamidofluorene and the 4-nitrophthalonitrile is 1:2, and the molar ratio of the anhydrous potassium carbonate to the bisphenol-bisamidofluorene is (1.5-2.5):1; and carrying out reaction for 12-16 hours at 85-95 DEG C, and carrying out distilled water washing and vacuum drying after the reaction ends, so as to obtain the self-catalyzed fluorenyl bisphthalonitrile resin monomer containing active amino. By utilizing a condensation reaction, a series of novel self-catalyzed fluorenyl bisphthalonitrile resin monomers containing active amino and aryl ether structures are synthesized, and the self-catalyzed cross-linking reaction of a phthalonitrile monomer is realized, so that the temperature of a curing reaction is lowered, and meanwhile, the resin is endowed with the characteristics of high temperature resistance and high carbon residual.
Description
Technical field
What the present invention relates to is a kind of organic compound, the present invention also relates to a kind of preparation method of organic compound.Specifically a kind of fluorenyl bi-phthalonitrile resin monomer and preparation method thereof.
Background technology
O-phthalonitrile resin received publicity since the eighties in 20th century, it is the class high-performance thermosetting resin being obtained by addition polymerization by phthalonitrile monomer, the network structure taking fragrant heterocycle as cross-linking set of its formation, in addition the existence of abundant phenyl ring in monomer backbone structure, thermostability and the thermo-oxidative stability of o-phthalonitrile resin excellence are given, in temperature mechanical property stable for extended periods of time during up to 371 DEG C, and have higher second-order transition temperature, its resistance to elevated temperatures is considerably beyond existing other high-performance thermosetting resins.Meanwhile, the chemical stability of bi-phthalonitrile resin polymkeric substance, flame retardant resistance, moistureproofness, processibility is also than more excellent, thereby is with a wide range of applications in high-tech sectors such as aerospace, boats and ships and microelectronics.But the heat cross-linking curing reaction of phthalonitrile in catalyst-free situation is very slow; even if (as 350 DEG C) are placed and within more than 20 hours, are also difficult to occur gel reaction at very high temperature; therefore need to add some catalyzer to promote the polymerization of cyano group; as can be obviously shortened rear curing time by catalyzer such as additional phenols, organic amine, acid anhydrides, organic acid/amine salt and metal-salts, can promote solidifying of phthalonitrile and derivative thereof.So in the research of curing reaction mechanism, the research of linking agent and selection are vital.And adopt small molecules linking agent volatile in solidification process, often cause the defect of material.At present, be subject to the general structure of bi-phthalonitrile resin monomer of extensive concern as follows:
In formula, A is at least a divalent group that contains aromatic hydrocarbons or heterocycle, and B is oxygen, sulphur or nitrogen-atoms.
Fluorenes molecule is rigid plane biphenyl structural, there is high-luminous-efficiency, good thermostability, light stability, chemical stability and be easy to the features such as processing, can be made into a series of polyimide resin, polycarbonate, epoxy resin and benzoxazine colophonies etc. with excellent heat stability, humidity resistance, dielectric properties, mechanical property, high transparent, high refractive index, be widely used in the fields such as matrix material, Electronic Packaging, insulating material, optical material.The people such as Achar are with 9, two (4-hydroxyphenyl) fluorenes of 9-and 4-nitrophthalonitrile are raw material, synthesize bi-phthalonitrile resin monomer (the Achar BN containing fluorenyl, Fohlen GM, Parker JA. Synthesis and Characterization of the Novel Type of PolymerizableBisphthalonitrile Monomers. Journal of Polymer Science:Part A:Polymer Chemistry, 1986,24:1997-2010).But in this monomer, only contain two aryl ethers structures, do not contain active amino, and do not introduce the performance of the curing and cured product of this monomer.Fluorenyl bi-phthalonitrile resin monomer structure is as follows:
Summary of the invention
The object of the present invention is to provide a kind of autocatalysis fluorenyl bi-phthalonitrile resin monomer containing active amino and aryl ethers structure.The present invention also aims to provide one can reduce curing reaction temperature, give the autocatalysis fluorenyl bi-phthalonitrile resin method for preparing monomer of high temperature resistant, the high carbon residue feature of resin simultaneously.
The object of the present invention is achieved like this:
Autocatalysis fluorenyl bi-phthalonitrile resin monomer of the present invention has following structure:
In formula: R is H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH (CH
3)
2, CH
2cH
2cH
2cH
3, OCH
3, OCH
2cH
3, OCH
2cH
2cH
3or OCH
2cH
2cH
2cH
3.
Autocatalysis fluorenyl bi-phthalonitrile resin monomer of the present invention is prepared in such a way: bis-phenol-diamine fluorenes, 4-nitrophthalonitrile, Anhydrous potassium carbonate and organic solvent are added in reaction vessel, the mol ratio of bis-phenol-diamine fluorenes and 4-nitrophthalonitrile is 1:2, the mol ratio of Anhydrous potassium carbonate and bis-phenol-diamine fluorenes is 1.5～2.5:1, at 85～95 DEG C, react 12～16 hours, after reaction finishes, through distilled water wash, vacuum-drying, obtain the autocatalysis fluorenyl bi-phthalonitrile resin monomer that contains active amino.
The preparation method of autocatalysis fluorenyl bi-phthalonitrile resin monomer of the present invention also has some technical characterictics like this:
1, described bis-phenol-diamine fluorenes is 2, 7-dihydroxyl-9, 9-pair-(4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-methyl-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-ethyl-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-propyl group-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-sec.-propyl-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-butyl-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-methoxyl group-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-oxyethyl group-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-propoxy--4-aminophenyl) fluorenes or 2, 7-dihydroxyl-9, 9-pair-(3-butoxy-4-aminophenyl) fluorenes.
2, described organic solvent is DMF (DMF) or dimethyl sulfoxide (DMSO) (DMSO).
The present invention is with 4-nitrophthalonitrile and 2, 7-dihydroxyl-9, two (4-aminophenyl) fluorenes of 9-, 2, 7-dihydroxyl-9, two (3-alkyl-4-aminophenyl) fluorenes or 2 of 9-, 7-dihydroxyl-9, 9-two (3-alkoxyl group-4-aminophenyl) is raw material, by condensation reaction, synthesize the autocatalysis fluorenyl bi-phthalonitrile resin monomer of series of new containing active amino and aryl ethers structure, by the amino katalysis to itrile group on fluorenes molecule, realize the autocatalysis crosslinking reaction of phthalonitrile monomer, thereby reduction curing reaction temperature, give resin high temperature resistant simultaneously, the feature of high carbon residue, be widely used in aerospace, the high-tech sector such as boats and ships and microelectronics.
Autocatalysis fluorenyl bi-phthalonitrile resin monomer structure of the present invention characterizes and 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 and membrane process, Sample Scan 4 times, resolving power 4cm
-1, sweep limit to 4000～500cm
-1, proton nmr spectra is mark in doing with tetramethylsilane (TMS), deuterochloroform (CDCl
3) make solvent.Polymkeric substance thermal performance test adopts differential scanning calorimeter (DSC, TA company of the U.S.), thermogravimetric analyzer (TGA, TA company of the U.S.).
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
By 14.53g(0.084mol) 4-nitrophthalonitrile, 15.98g(0.042mol) 2; 7-dihydroxyl-9; 9-is two-(4-aminophenyl) fluorenes, 11.60g(0.084mol) and Anhydrous potassium carbonate is dissolved in 80mL DMF; then insert in the 250mL there-necked flask with magnetic agitation rotor, thermometer and reflux exchanger; pass into nitrogen protection; be warming up to 90 DEG C; isothermal reaction 14 hours; after reaction finishes; with the distilled water wash of 500mL 5～6 times; vacuum-drying, obtains dark yellow powder, yield 86.2%.
Proton nmr spectra test result (500M, DMSO-d
6, ppm): 3.70(s, 4H ,-NH
2), 6.55～6.57 and 6.90～6.92(d, 8H, the H proton in aminophenyl on phenyl ring), 7.05～7.81 (m, 12H, the H protons on fluorenes and phthalonitrile on phenyl ring).Examination of infrared spectrum result (KBr, cm
-1): 3446 and 3379 (N-H stretching vibrations), 2226(itrile group C-N stretching vibration), 1482(phenyl ring 1,2,4-tri-replaces) and, 1277 and 1062 (C-O asymmetric and symmetrical stretching vibration), confirm that gained sample is target product.
This itrile group resin monomer is put into electric drying oven with forced convection, adopt programmed temperature method to carry out thermofixation to monomer, curing cycle is: 210 DEG C/6h, 240 DEG C/3h, 270 DEG C/3h, 300 DEG C/4h, obtain poly-o-phthalonitrile resin, through DSC and TGA test, the second-order transition temperature of polymkeric substance (is abbreviated as T
g, as follows) and be that 337 DEG C, weightless 5% and 10% corresponding heat decomposition temperature (are abbreviated as T
5and T
10, as follows) and 900 DEG C at carbon yield (be abbreviated as Y
c) be respectively 527 DEG C, 571 DEG C and 78.4%.
Embodiment 2
By 10.38g(0.06mol) 4-nitrophthalonitrile, 12.24g(0.03mol) 2,7-dihydroxyl-9, two (3-methyl-4-aminophenyl) fluorenes of 9-, 8.28g(0.06mol) Anhydrous potassium carbonate is dissolved in 100Ml DMSO, then be placed in 250ml there-necked flask, pass into nitrogen, be warming up to 95 DEG C, isothermal reaction 11 hours.Reacted the rear distilled water wash with 500mL 5～6 times, vacuum-drying, obtains dark yellow powder, yield 90.4%.
Proton nmr spectra test result (500M, DMSO-d
6, ppm): 2.05(s, 6H ,-CH
3), 3.61(s, 4H ,-NH
2), 6.53～6.57 and 6.78～6.81 (d, 4H, two adjacent hydrogen protons on phenyl ring in aminophenyl), 6.77 (s, 2H, single H protons on phenyl ring in aminophenyl), 7.06～7.81 (m, 12H, the H protons on fluorenes and phthalonitrile on phenyl ring).Examination of infrared spectrum result (KBr, cm
-1): 3458 and 3381 (N-H stretching vibrations), 2232(itrile group C-N stretching vibration), 1504(phenyl ring 1,2,4-tri-replaces) and, 1253 and 1086 (C-O asymmetric and symmetrical stretching vibration), confirm that gained sample is target product.
Condition of cure is with embodiment 1, the T of poly-o-phthalonitrile resin
gbe 335 DEG C, T
5, T
10y during with 900 DEG C
cvalue is respectively 504 DEG C, 547 DEG C and 75.5%.
Embodiment 3
Except raw material 2,7-dihydroxyl-9,9-pair-(4-aminophenyl) fluorenes replaces with 2,7-dihydroxyl-9,9-pair-(3-butyl-4-aminophenyl) fluorenes, consumption is 20.69g(0.042mol) outside, other condition, with embodiment 1, finally obtains dark yellow powder, yield 83.7%.
Proton nmr spectra test result (500M, DMSO-d
6, ppm): 0.86～0.93(t, 6H ,-CH
3), 1.31～1.37 and 1.58～1.65(m, 8H ,-CH
2-), 2.55～2.63(t, 4H, Ar-CH
2-), 3.2(s, 4H ,-NH
2), 6.50～6.53 and 6.73～6.76 (d, 4H, two adjacent hydrogen protons on phenyl ring in aminophenyl), 6.75 (s, 2H, single H protons on phenyl ring in aminophenyl), 7.04～7.80 (m, 12H, the H protons on fluorenes and phthalonitrile on phenyl ring).Examination of infrared spectrum result (KBr, cm
-1): 3447 and 3380 (N-H stretching vibrations), 2227(itrile group C-N stretching vibration), 1496(phenyl ring 1,2,4-tri-replaces) and, 1244 and 1085 (C-O asymmetric and symmetrical stretching vibration), confirm that gained sample is target product.
Condition of cure is with embodiment 1, the T of poly-o-phthalonitrile resin
gbe 310 DEG C, T
5, T
10y during with 900 DEG C
cvalue is respectively 491 DEG C, 536 DEG C and 70.3%.
Embodiment 4
Except raw material 2,7-dihydroxyl-9,9-pair-(4-aminophenyl) fluorenes replaces with 2,7-dihydroxyl-9,9-pair-(3-methoxyl group-4-aminophenyl) fluorenes, consumption is 18.51g(0.042mol) outside, other condition, with embodiment 1, finally obtains orange-yellow powder, yield 88.2%.
Proton nmr spectra test result (500M, DMSO-d
6, ppm): 3.35(s, 6H ,-OCH
3), 3.66(s, 4H ,-NH
2), 6.51～6.56 and 6.76～6.78 (d, 4H, two adjacent hydrogen protons on phenyl ring in aminophenyl), 6.74 (s, 2H, single H protons on phenyl ring in aminophenyl), 7.05～7.79 (m, 12H, the H protons on fluorenes and phthalonitrile on phenyl ring).Examination of infrared spectrum result (KBr, cm
-1): 3450 and 3379 (N-H stretching vibrations), 2230(itrile group C-N stretching vibration), 1498(phenyl ring 1,2,4-tri-replaces) and, 1249 and 1088 (C-O asymmetric and symmetrical stretching vibration), confirm that gained sample is target product.
Condition of cure is with embodiment 1, the T of poly-o-phthalonitrile resin
gbe 328 DEG C, T
5, T
10y during with 900 DEG C
cvalue is respectively 510 DEG C, 551 DEG C and 76.8%.
Claims (4)
1. an autocatalysis fluorenyl bi-phthalonitrile resin monomer, is characterized in that having following structure:
In formula: R is H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH (CH
3)
2, CH
2cH
2cH
2cH
3, OCH
3, OCH
2cH
3, OCH
2cH
2cH
3or OCH
2cH
2cH
2cH
3.
2. the preparation method of an autocatalysis fluorenyl bi-phthalonitrile resin monomer, it is characterized in that: bis-phenol-diamine fluorenes, 4-nitrophthalonitrile, Anhydrous potassium carbonate and organic solvent are added in reaction vessel, the mol ratio of bis-phenol-diamine fluorenes and 4-nitrophthalonitrile is 1:2, the mol ratio of Anhydrous potassium carbonate and bis-phenol-diamine fluorenes is 1.5～2.5:1, at 85～95 DEG C, react 12～16 hours, after reaction finishes, through distilled water wash, vacuum-drying, the structural formula that has that obtains containing active amino is
autocatalysis fluorenyl bi-phthalonitrile resin monomer, wherein R is H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH (CH
3)
2, CH
2cH
2cH
2cH
3, OCH
3, OCH
2cH
3, OCH
2cH
2cH
3or OCH
2cH
2cH
2cH
3.
3. the preparation method of autocatalysis fluorenyl bi-phthalonitrile resin monomer according to claim 2, it is characterized in that: described bis-phenol-diamine fluorenes is 2, 7-dihydroxyl-9, 9-pair-(4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-methyl-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-ethyl-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-propyl group-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-sec.-propyl-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-butyl-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-methoxyl group-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-oxyethyl group-4-aminophenyl) fluorenes, 2, 7-dihydroxyl-9, 9-pair-(3-propoxy--4-aminophenyl) fluorenes or 2, 7-dihydroxyl-9, 9-pair-(3-butoxy-4-aminophenyl) fluorenes.
4. according to the preparation method of the autocatalysis fluorenyl bi-phthalonitrile resin monomer described in claim 2 or 3, it is characterized in that: described organic solvent is DMF or dimethyl sulfoxide (DMSO).
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367774A (en) * | 2008-09-27 | 2009-02-18 | 哈尔滨工程大学 | Fluorenyl bi-benzoxazine monomer and method of preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367774A (en) * | 2008-09-27 | 2009-02-18 | 哈尔滨工程大学 | Fluorenyl bi-benzoxazine monomer and method of preparing the same |
Non-Patent Citations (2)
| Title |
|---|
| Achar et al.Synthesis and Characterization of the Novel Type of PolymerizableBisphthalonitrile Monomers.《Journal of Polymer Science: Part A: Polymer Chemistry》.1986,第24卷1997-2010. * |
| Synthesis and Characterization of the Novel Type of PolymerizableBisphthalonitrile Monomers;Achar et al;《Journal of Polymer Science: Part A: Polymer Chemistry》;19861231;第24卷;1997-2010 * |
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