CN101307013A - Aromatic diamine with phthalonitrile pendant group, preparation method thereof and polyimides or polyamide prepared therefrom - Google Patents
Aromatic diamine with phthalonitrile pendant group, preparation method thereof and polyimides or polyamide prepared therefrom Download PDFInfo
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Abstract
The invention discloses an aromatic diamine containing o-phthalonitrile side group. The structure formula of the aromatic diamine is shown as the right formula. The invention also discloses a method for preparing the aromatic diamine and polyimide and daiamid which are prepared by taking the aromatic diamine containing the o-phthalonitrile side group as one of raw materials. The o-phthalonitrile side group in the aromatic diamine is positioned on the side chain, thereby adjusting the degree of crosslinking with adjusting the polymer molecular weight and widening the application of the polyimide and the daiamid in a thick-wall composite material or a composite material element with a complicated shape and the fields of membrane material and fiber.
Description
Technical field
The invention belongs to aromatic diamine and preparation method thereof and polyimide or polymeric amide technical field, be specifically related to the aromatic diamine and preparation method thereof of phthalonitrile pendant group and by the aromatic diamine of phthalonitrile structure phthalonitrile pendant group polyimide or polymeric amide as the monomer preparation.
Background technology
Polyimide (PI) is the high-performance polymer that a class main chain contains imide ring, because it has excellent thermostability, mechanical property, unreactiveness, dielectric properties and radiation resistance, has obtained widespread use with commercial form such as film, coating, fiber, plastics, tackiness agent and polymer matrix composites in high-tech sectors such as aerospace, electronic industries already.Polyimide utilizes aromatic dianhydride and diamines by the polycondensation preparation, and its building-up process is as follows:
Polyimide mainly can be divided into non-crosslinked polyimide and Thermocurable polyimide.Compare with the non-crosslinked polyimide, Thermocurable polyimide has good processibility, and can keep polyimide excellent comprehensive performance relatively.At present, researching and developing more Thermocurable polyimide is to contain acetylene group (U.S.Pat.No.4,098,767) and phenylacetylene group (U.S.Pat.No.5,412,066) polyimide, the polyimide that contains acetylene group, because of the melt temperature of the temperature of reaction of acetylene group and imide oligomer thing overlapping, make its processing temperature window very narrow, thereby limited its application in casting heavy wall or complicated shape composite product, and contained the polyimide of phenylacetylene group, because the curing exotherm of phenylacetylene group wherein is fast, and poor controllability, make the heavy wall composite product of making cause its thermal gradient excessive easily, cause unrelieved stress, make material present fragility and easy to crack.In addition, need at the anhydrous and oxygen-free conditional operation owing to prepare the triphenyl phosphorus/palladium ligand catalyst that uses in the polyimide of acetylene END CAPPED GROUP and phenylacetylene-capped base, thereby the preparation condition harshness, cost is very high, has limited the degree of depth and the range of its application.
Solidifying the phthalocyanine resin that is obtained by phthalonitrile-terminated derivative is another kind of high performance material with excellent mechanical behavior under high temperature.Though the cross-linking and curing reaction of phthalonitrile is controlled, can be applicable to the processing request of different composite material, and the resin after solidifying has excellent thermal characteristics and mechanical property (Keller T.M.PolymerComposites, 2004,25,554), but because of the research of the phthalocyanine modified polyimide of reports such as Keller mainly concentrates on phthalonitrile-terminated type polyimide (Keller T.M.Polymer, 1993,34,952.Keller T.M.Polymer Communications, 1991,32,2), its structure is as follows:
And also there is following problem in phthalonitrile-terminated type polyimide:
(1) because the phthalonitrile unit is in the polymkeric substance end of the chain, its reactive behavior is subject to the molecular weight of polymkeric substance, molecular weight is too big, the phthalonitrile reactive behavior reduces, and is difficult to form effectively crosslinked (U.S.Pat.No.5,132,396), molecular weight is too small, and the cross-linking density of polymkeric substance is excessive again, will make polymkeric substance present bigger fragility.
(2) existing phthalonitrile-terminated type polyimide, its molecular weight are usually all in the 2000g/mol scope, so its film-forming properties is relatively poor, has limited its application in film material and fiber art.
Similar with polyimide, also be a class high-performance polymer by aromatic series diacid chloride and diamines by the aromatic polyamide that polycondensation prepares, it is synthetic and general structure is as follows:
Because traditional common infusibility indissoluble of aromatic polyamide is difficult to processing, thereby people have studied a lot of modified methods to improve the processibility of polymeric amide.These modified methods mainly are included on the main chain of polymeric amide and introduce side group (Meyer.M.R.Macromolecules, 24,642), though it is processibility that these means can significantly improve the organic soluble of polymeric amide, but because the reduction of polyimide molecule chain rigidity, thereby sacrificed thermal characteristics, mechanical property and the solvent resistance of polymeric amide excellence, limited the range of application of polymeric amide.
Summary of the invention
One of purpose of the present invention is the problem that exists at prior art, and a kind of aromatic diamine that can be used to prepare the new phthalonitrile pendant group of polyimide and polymeric amide is provided.
Two of purpose of the present invention provides a kind of method for preparing the aromatic diamine of above-mentioned phthalonitrile pendant group.
Three of purpose of the present invention provides a kind of polyimide of the phthalonitrile pendant group that is formed by the aromatic diamine and the aromatic dianhydride compound of phthalonitrile pendant group.
Four of purpose of the present invention provides a kind of polyimide of the phthalonitrile pendant group that is formed by the aromatic diamine and the diacid chloride compound of phthalonitrile pendant group.
The aromatic diamine of phthalonitrile pendant group provided by the invention, the general structure of this aromatic diamine is:
The aromatic diamine of above-described phthalonitrile pendant group specifically can be any in following general structure I, II, the III class monomer:
I class monomer
R
1＝-O-
II class monomer
III class monomer
The method of the aromatic diamine of the phthalonitrile pendant group that preparation provided by the invention is above-mentioned, wherein the reaction equation of the monomer 3 in I class monomer and the II class monomer, preparation method's processing step and condition are as follows:
Earlier component A and 4 (3)-nitrophthalonitriles are calculated in molar ratio as 0.3-1.2: 1 is dissolved in the solvent orange 2 A fully, adding with 4-nitrophthalonitrile molar ratio computing again is the catalyst A of 1-3, and at the room temperature-160 ℃ following 4-24h that stirs, decompressing and extracting solvent orange 2 A then, washing promptly gets intermediate compound I-1 after the separation drying; Obtaining I-1 intermediate and solvent B are added in the reactor, under nitrogen atmosphere, add the catalyst B of counting 0.5-10% by the quality of intermediate compound I-1,, filter, drain solvent B and get product I-2 at room temperature-80 ℃ reaction 8-48h.
The reaction equation of the monomer 4,5 in the II class monomer, preparation method's processing step and condition are as follows:
Earlier with o-Xylol and B component 0.9-4.2 in molar ratio: 1 is dissolved in the solvent C fully, add with the molar ratio computing of B component is the catalyzer C of 1.1-8 again, at 10-50 ℃ of reaction 1-6h, pour in the dilute acid soln of mass concentration＜20% and precipitate, filter or separatory drain after the solvent C the II-1 intermediate; With mass concentration is the nitric acid of 30-60% and II-1 intermediate 4-50 in molar ratio: 1 adds in the withstand voltage reactor of sealing, at 120-180 ℃ of reaction 2-8h, filter behind the washing and drying the II-2 intermediate; With urea and II-2 intermediate 1-16 in molar ratio: 1 adds and makes it dissolving among the solvent D fully, and at 120-160 ℃ of reaction 0.5-4h down, drain behind the solvent D the II-3 intermediate; With amidation reagent and II-3 intermediate 4-35 in molar ratio: 1 mixes, or the II-3 intermediate is dissolved in feeds amidation reagent among the solvent E more earlier, at 15-80 ℃ of reaction 1-20h, behind the filtration drying the II-4 intermediate; The II-4 intermediate is dissolved among the solvent F fully, adding with II-4 intermediate mol ratio is 2-40 again: 1 dewatering agent or will be 2-40 with II-4 intermediate mol ratio earlier: 1 dewatering agent mixes with solvent F, solvent F consumption will make the II-4 dissolving fully, again the II-4 intermediate is added wherein, behind 20-90 ℃ of reaction 2-10h, pour in the big water gaging then and precipitate, get the II-5 intermediate behind the filtration drying; The solid content 0.5-20% (g/ml) that II-5 intermediate, solvent G is pressed II-5 adds in the reactor, under nitrogen atmosphere, add the catalyzer D that counts 0.5-10% with II-5 intermediate quality, at room temperature-80 ℃ following reaction 4-48h, filter then, drain solvent G and get product II-6.
The monomeric reaction equation of III class, preparation method's processing step and condition are as follows:
Earlier will be with 3,5-dinitrobenzoyl chloride molar ratio computing is 1: the component C of 0.9-1.5 adds among the solvent H dissolves it fully, add and 3 again, 5-dinitrobenzoyl chloride molar ratio computing is 1: the acid binding agent of 0.9-1.5, add 3,5 dinitrobenzoylchloride at last, and at 10-40 ℃ of following stirring reaction 4-24h, pour into again in the big water gaging and precipitate, get product III-1 after the separation drying; Will the III-1 intermediate add among the solvent I it will be dissolved fully, and under nitrogen atmosphere, add the catalyzer E that counts 0.5-10% with III-1 intermediate quality,, filter, drain solvent I and get product III-2 at ℃ following reaction 4-48h of room temperature-80.
Used solvent orange 2 A is N in the aforesaid method, any in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO) or the N-Methyl pyrrolidone (NMP); Solvent B is any in dehydrated alcohol, DMF, tetrahydrofuran (THF) (THF), ethyl acetate or the acetone; Solvent C is o-Xylol, methylene dichloride, 1, any in 2-ethylene dichloride or the dithiocarbonic anhydride; Solvent D is N, any among dinethylformamide DMF, N,N-dimethylacetamide DMAc, dimethyl sulfoxide (DMSO) DMSO or the N-Methyl pyrrolidone NMP; Solvent E is methyl alcohol, ethylene glycol, N, any among the dinethylformamide DMF; Solvent F is DMF or N, accelerine; Solvent G dehydrated alcohol, N, any in dinethylformamide DMF, tetrahydrofuran THF, ethyl acetate (EA), the acetone.
Used catalyst A is Anhydrous potassium carbonate or anhydrous sodium carbonate in the aforesaid method; It is 10% or 5%Pd/C that catalyst B, D and E are massfraction; Catalyzer C is any in aluminum trichloride (anhydrous), anhydrous tri-chlorination zinc or the FERRIC CHLORIDE ANHYDROUS.
Used amidation reagent is strong aqua or ammonia in this method; Used dilute acid soln is any in dilute hydrochloric acid, dilute sulphuric acid or the dilute phosphoric acid; Used dewatering agent is thionyl chloride or phosphorus oxychloride; Used acid binding agent is any in pyridine, triethylamine, propylene oxide or the 4-Dimethylamino pyridine (DMAP).
Need to prove the concrete raw material 3 among the preparation I class monomer used component A especially, 5-dinitrophenol(DNP) and 4,4 '-dinitrobenzene-2,2 '-dihydroxybiphenyl synthetic sees document: [Wang D.H; Shen Z.H; Guo M.M; ChengS.Z.D; Harris F.W.Macromolecules, 2007,40,889.].Prepare 3 among the used component A of I class monomer, 5-dinitrobenzene-4 '-dihydroxy benaophenonel is then by following synthesis technique preparation:
Earlier with 3,5-dinitrobenzoyl chloride and methyl-phenoxide or phenyl ethyl ether be 0.9-1.2 in molar ratio: 1 is dissolved among the solvent J fully, adding and methyl-phenoxide or phenyl ethyl ether molar ratio computing are the catalyzer F of 1.1-4 again, and at 10-50 ℃ of following reaction 2-6h, pour into then in mass concentration＜20% dilute acid soln, filtration or separatory get product after draining solvent.
Wherein used solvent J is benzene second (first) ether, methylene dichloride, 1, any in 2-ethylene dichloride, the dithiocarbonic anhydride; Used catalyzer F is any in aluminum trichloride (anhydrous), anhydrous tri-chlorination zinc, the FERRIC CHLORIDE ANHYDROUS; Dilute acid soln is any in dilute hydrochloric acid, dilute sulphuric acid, the dilute phosphoric acid.
The polyimide of phthalonitrile pendant group provided by the invention is to be formed by the aromatic diamine of synthetic phthalonitrile pendant group of the present invention and aromatic dianhydride compound, and the structural formula that its reaction generates is as follows:
N=8-200 wherein, the intrinsic viscosity of this polyimide is 0.2-2.0dL/g, number-average molecular weight is 5000-100000g/mol.
Wherein used aromatic dianhydride compd A is equal benzene four acid anhydrides (PMDA), phenyl ether dianhydride (ODPA), biphenyl dianhydride (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 4,4-(hexafluoro sec.-propyl) diphthalic anhydrides (6FDA), 3,3 ', 4, any in 4 '-diphenylsulfone acid dianhydride (SDPA), n=8-200, the intrinsic viscosity of this polyimide is 0.2-2.0dL/g, and number-average molecular weight is 5000-120000g/mol.
The polyimide of above-mentioned phthalonitrile pendant group provided by the invention is by following concrete grammar synthetic:
The aromatic diamine that in polar solvent, adds the above-mentioned phthalonitrile side chain of the present invention's preparation, being stirred to it dissolves fully, adding and diamines mol ratio are 1: 1 aromatic dianhydride compound again, adding is 4-20 with the diamines mol ratio behind the stirring at room 4-24h: 1 dewatering agent, at room temperature-150 ℃ following reaction 2-24h, reaction solution is poured in the precipitation agent, promptly got the polyimide of phthalonitrile pendant group after the separation drying.
Used aromatic dianhydride compound is equal benzene four acid anhydrides (PMDA), phenyl ether dianhydride (ODPA), biphenyl dianhydride (BPDA), 3 in the above-mentioned synthetic method, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 4,4-(hexafluoro sec.-propyl) diphthalic anhydrides (6FDA), 3,3 ', 4, any in 4 '-diphenylsulfone acid dianhydride (SDPA); Used polar solvent is any among DMF, DMSO, DMAc, the NMP in the above-mentioned synthetic method; Used precipitation agent is any in water, methyl alcohol, the ethanol in the above-mentioned synthetic method; Used dewatering agent is any in physics dewatering agent or the chemical dehydrator in the above-mentioned synthetic method.The physics dewatering agent is toluene, dimethylbenzene, chlorobenzene or N, N-di-n-butyl aniline; Chemical dehydrator is any in diacetyl oxide/pyridine, diacetyl oxide/triethylamine, acetic anhydride/acetic acid sodium, phthalic anhydride/pyridine, trifluoroacetic anhydride/triethylamine, trifluoroacetic anhydride/pyridine, dicyclohexylcarbodiimide DCC, sulfur oxychloride or the phosphorus oxychloride.
The polymeric amide of phthalonitrile pendant group provided by the invention is to be formed by the aromatic diamine of synthetic phthalonitrile pendant group of the present invention and diacid chloride compound, and the structural formula that its reaction generates is as follows:
N=9-200 wherein, the intrinsic viscosity of this polymeric amide is 0.2-20dL/g, number-average molecular weight is 5000-120000g/mol.
Wherein used fragrant diacid chloride compd A is p-phthaloyl chloride (TPC), m-phthaloyl chloride (IPC), 2, in 6-naphthalene dimethyl chloride (NPDC), biphenyl dimethyl chloride (BPDC), phenyl ether dimethyl chloride (ODC), the sulfobenzide dimethyl chloride (SDC) any
The polymeric amide of above-mentioned phthalonitrile pendant group provided by the invention is by following concrete grammar synthetic:
In polar solvent, add the present invention's preparation above-mentioned phthalonitrile side chain aromatic diamine and with the mol ratio of this aromatic diamine be 2-4: 1 acid binding agent, after being stirred to aromatic diamine and dissolving fully, adding and aromatic diamine mol ratio are 1: 1 fragrant diacid chloride compound again, after-20 ℃ to 30 ℃ are stirred 4-24h, reaction solution is poured in the precipitation agent, got the polymeric amide of phthalonitrile pendant group after the separation drying.
Used fragrant diacid chloride compd A is p-phthaloyl chloride (TPC), m-phthaloyl chloride (IPC), 2 in the above-mentioned synthetic method, any in 6-naphthalene dimethyl chloride (NPDC), biphenyl dimethyl chloride (BPDC), phenyl ether dimethyl chloride (ODC), the sulfobenzide dimethyl chloride (SDC); Used polar solvent is any among DMF, DMSO, DMAc, the NMP in the above-mentioned synthetic method; Used precipitation agent is any in water, methyl alcohol, the ethanol in the above-mentioned synthetic method; Used acid binding agent is any in pyridine, triethylamine, the propylene oxide in the above-mentioned synthetic method.
Compared with the prior art the present invention has the following advantages:
1, the aromatic diamine of phthalonitrile side chain provided by the invention is not have in the prior art, thereby has filled up the blank of this aromatic diamine, provides a class new raw material for the derivative by phthalonitrile solidifies the phthalocyanine resin that is obtained.
2, owing to contained phthalonitrile unit in the aromatic diamine provided by the invention is to be positioned on the side chain, thereby its activity of cross-linking reaction can not be subject to the molecular weight of polymkeric substance, and also can regulate and control the degree of crosslinking of polymkeric substance by the regulation and control polymericular weight, can expand the application of polyimide and polymeric amide in heavy wall matrix material or complicated shape composite product field.
3, because the aromatic diamine of phthalonitrile side chain provided by the invention also can carry out copolymerization with the conventional fragrant family diamines of different structure, thereby can be by regulate and control the processibility and the use properties of polymkeric substance to the selection of copolymerization composition.
4,, thereby widened the range of application of the polyimide of usefulness phthalocyanine modification in film material and fiber art owing to be much higher than existing phthalonitrile-terminated type polyimide with the molecular weight of the polyimide of the aromatic diamine modification of phthalonitrile side chain provided by the invention preparation.
What 5, the polymeric amide that provides clearly owing to basis was introduced on main chain is the side group of phthalonitrile, thereby when raising polymeric amide organic soluble is processibility, can also utilize the crosslinking reaction of phthalonitrile to obtain thermal characteristics, mechanical property and all very excellent polymeric amide of solvent resistance, and then can enlarge the range of application of polymeric amide.
6, the preparation route from the direct synthesizing imide of phthalic acid provided by the invention is compared the step that traditional synthetic route has reduced synthesizing imide, the reaction conditions gentleness, reduced preparation cost, and easy and simple to handle, be easy to control, thereby be more suitable for industrial production.
Embodiment
Provide embodiment below so that the invention will be further described.Be necessary to be pointed out that at this following examples can not be interpreted as limiting the scope of the invention; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to protection domain of the present invention.
In addition, intrinsic viscosity that what deserves to be explained is following examples gained polyimide, polymeric amide is that DMAc is a solvent, is mixed with the solution that concentration is 0.5g/dL, with the intrinsic viscosity number η of dark type viscometer at 30 ℃ of these polymkeric substance of test
Inh, its number-average molecular weight is measured by gel chromatography (GPC).
Embodiment 1
Present embodiment is monomer 1 synthetic in the I class monomer and prepares the embodiment of polyimide and polymeric amide respectively with it.
Earlier with 1mol 3,5-dinitrophenol(DNP), 1mol 4 (3)-nitrophthalonitriles are dissolved among the 1L DMF fully, add the 2mol Anhydrous potassium carbonate again, and at room temperature stir decompressing and extracting solvent behind the 24h, and washing promptly gets intermediate compound I-1 after separating drying; 1g I-1 intermediate and 20ml dehydrated alcohol are added in the reactor, under nitrogen atmosphere, add again and count 5% Pd/C (concentration 5%) by the quality of intermediate compound I-1,, filter, drain solvent and get monomer 1 at room temperature reaction 48h.
FTIR (the cm of the monomer that obtains 1
-1): 3446,3363 (N-H), 3036 (C=C-H), 2233 (CN), 1487-1607 (C=C), 1251 (C-O-C).
1H?NMR(DMSO-d
6ppm)：8.05-8.08(d，1H，Ar-H)，7.71-7.72(d，1H，Ar-H)，7.32-7.36(dd，1H，Ar-H)，6.30-6.35(dd，2H，Ar-H)，6.22-6.25(m，1H，Ar-H)，4.3(s，4H，NH
2)。Ultimate analysis calculated value: C, 67.19; H, 4.03; N, 22.39; O, 6.39 element measured value: C, 67.18; H, 3.99; N:22.40; O, 6.43.
Adding monomer 1 in polar solvent DMF is stirred to it and dissolves fully, adding and monomer 1 mol ratio are 1: 1 aromatic dianhydride Compound P MDA again, adding and monomer 1 mol ratio are 5: 1 toluene behind the stirring at room 12h, react 12h down at 120 ℃, reaction solution is poured in the methyl alcohol, promptly get the polyimide of phthalonitrile pendant group after the separation drying, the η that records
Inh=0.5dL/g, Mn=32000.
After adding monomer 1 is stirred to dissolving fully in polar solvent DMF, add mol ratio with monomer 1 again and be 2: 1 the acid binding agent pyridine and with monomer 1 mol ratio be 1: 1 fragrant diacid chloride compound TPC, after at room temperature stirring 12h reaction solution is poured in the precipitation agent methanol, get the polymeric amide of phthalonitrile pendant group after the separation drying, the η that records
Inh=0.3dL/g, Mn=26000.
Embodiment 2
Present embodiment is monomer 2 synthetic in the I class monomer and prepares the embodiment of polyimide and polymeric amide respectively with it.
First with 0.3mol 4,4 '-dinitrobenzene-2,2 '-dihydroxybiphenyl, 1mol 4 (3)-nitrophthalonitriles are dissolved among the 800ml NMP fully, add the 3mol anhydrous sodium carbonate again, and 80 ℃ down stir 12h after the decompressing and extracting solvent, washing promptly gets intermediate compound I-1 after separating drying; 1g I-1 intermediate and 20ml THF are added in the reactor, under nitrogen atmosphere, add again and count 0.5% Pd/C (concentration 10%) by the quality of intermediate compound I-1,, filter, drain solvent and get monomer 2 at 40 ℃ of reaction 24h.
FTIR (the cm of the monomer that obtains 2
-1): 3455,3371 (N-H), 3045 (C=C-H), 2233 (CN), 1473-1628 (C=C), 1088 (C-O-C), 1248 (C-O-C).
1H?NMR(DMSO-d
6ppm)：8.05-8.08(d，2H，Ar-H)，7.71-7.72(d，2H，Ar-H)，7.32-7.50(m，4H，Ar-H?)，6.25-6.28(m，2H，Ar-H)，6.18-6.20(d，2H，Ar-H)，5.01(s，4H，NH
2)。Ultimate analysis calculated value: C, 71.79; H, 3.44; N, 17.94; O, 6.83 element measured value: G, 71.80; H, 3.40; N:17.89; O, 6.91.
Adding monomer 2 in polar solvent DMAc is stirred to it and dissolves fully, adding and monomer 2 mol ratios are 2: 2 aromatic dianhydride compound ODPA again, adding and monomer 2 mol ratios are diacetyl oxide/pyridine of 4: 1 behind the stirring at room 8h, at room temperature react 24h, reaction solution is poured in the water, promptly get the polyimide of phthalonitrile pendant group after the separation drying, the η that records
Inh=0.2dL/g, Mn=6000.
After adding monomer 2 is stirred to dissolving fully in polar solvent DMAc, add mol ratio with monomer 2 again and be 3: 1 the acid binding agent triethylamine and with monomer 2 mol ratios be 2: 2 fragrant diacid chloride Compound I PC, after 30 ℃ are stirred 4h down, reaction solution is poured in the precipitation agent water, get the polymeric amide of phthalonitrile pendant group after the separation drying, the η that records
Inh=0.21dL/g, Mn=5100.
Embodiment 3
Present embodiment is monomer 3 synthetic in the II class monomer and prepares the embodiment of polyimide and polymeric amide respectively with it.
Earlier with 3,5-dinitrobenzoyl chloride and methyl-phenoxide were dissolved in the 2000ml methylene dichloride in 0.9: 1 in molar ratio fully, adding and methyl-phenoxide molar ratio computing are 4 aluminum trichloride (anhydrous) again, and at 10 ℃ of following reaction 6h, pour into then in mass concentration 20% dilute hydrochloric acid solution, separatory gets product 3,5-dinitrobenzene-4 '-dihydroxy benaophenonel after draining solvent.
Or
Earlier with 3,5-dinitrobenzoyl chloride and phenyl ethyl ether were dissolved in the 3000ml dithiocarbonic anhydride in 1: 1 in molar ratio fully, adding and phenyl ethyl ether molar ratio computing are 1: 1.1 anhydrous tri-chlorination zinc again, and at 30 ℃ of following reaction 3h, pour into then in mass concentration 5% dilution heat of sulfuric acid, separatory gets product 3,5-dinitrobenzene-4 '-dihydroxy benaophenonel after draining solvent.
Or
Earlier with 3,5-dinitrobenzoyl chloride and phenyl ethyl ether were dissolved in the phenyl ethyl ether solvent of 3mol in 1.2: 1 in molar ratio fully, adding and phenyl ethyl ether molar ratio computing are 1: 3 FERRIC CHLORIDE ANHYDROUS again, and at 50 ℃ of following reaction 2h, pour into then in mass concentration 10% dilute phosphoric acid solution, separatory gets product 3,5-dinitrobenzene-4 '-dihydroxy benaophenonel after draining solvent.
Gained 3, the FTIR (cm of 5-dinitrobenzene-4 '-dihydroxy benaophenonel
-1): 3251-3352 (OH), 1650 (C=O), 1537,1346 (NO
2).
1H?NMR(DMSO-d
6ppm)：10-10.5(s，1H，OH)，9.31(dd，1H，Ar-H)，9.01-9.10(d，2H，Ar-H)，7.92-8.03(m，2H，Ar-H)，6.83(d，2H，Ar-H)。Ultimate analysis calculated value: C, 54.18; H, 2.80; N, 9.72; O, 33.31 element measured value: C, 54.20; H, 2.81; N:9.68; O, 33.27.
Earlier with above prepared 1.2mol 3,5-dinitrobenzene-4 '-dihydroxy benaophenonel, 1mol 4 (3)-nitrophthalonitriles are dissolved among the 1200ml DMSO fully, add the 1mol Anhydrous potassium carbonate again, and 160 ℃ down stir 4h after the decompressing and extracting solvent, washing promptly gets intermediate compound I-1 after the separation drying; 1g I-1 intermediate and 15ml DMF are added in the reactor, under nitrogen atmosphere, add again and count 10% Pd/C (concentration 5%) by the quality of intermediate compound I-1,, filter, drain solvent and get monomer 3 at 80 ℃ of reaction 8h.
FTIR (the cm of the monomer that obtains 3
-1): 3450,3368 (N-H), 2231 (CN), 1660 (C=O), 1248 (C-O-C).
1H?NMR(DMSO-d
6ppm)：8.06-8.10(d，1H，Ar-H)，7.72-7.75(d，1H，Ar-H)，7.35-7.40(dd，1H，Ar-H)，7.68(dd，2H，Ar-H)，7.02(dd，2H，Ar-H)，6.28-6.30(dd，2H，Ar-H)，6.22-6.25(m，1H，Ar-H)，4.2(s，4H，NH
2)。Ultimate analysis calculated value: C, 71.18; H, 3.98; N, 15.81; O, 9.03 element measured value: C, 71.17; H, 3.95; N:15.82; O, 9.06.
Adding monomer 3 in polar solvent DMSO is stirred to it and dissolves fully, adding and monomer 3 mol ratios are 3: 3 aromatic dianhydride compound OBPDA again, adding and monomer 3 mol ratios are diacetyl oxide/triethylamine of 6: 1 behind the stirring at room 24h, react 8h down at 50 ℃, reaction solution is poured in the ethanol, promptly get the polyimide of phthalonitrile pendant group after the separation drying, the η that records
Inh=1.0dL/g, Mn=88200.
After adding monomer 3 is stirred to dissolving fully in polar solvent DMSO, add mol ratio with monomer 2 again and be 4: 1 acid binding agent oxyethane and with monomer 3 mol ratios be 3: 3 fragrant diacid chloride compound N PDC, after-20 ℃ are stirred 24h down, reaction solution is poured in the precipitation agent ethanol, get the polymeric amide of phthalonitrile pendant group after the separation drying, the η that records
Inh=1.2dL/g, Mn=78900.
Embodiment 4
Present embodiment is monomer 4 synthetic in the II class monomer and prepares the embodiment of polyimide and polymeric amide respectively with it.
Earlier with o-Xylol and 3, the 5-dinitrobenzoyl chloride was dissolved in the methylene dichloride in 2: 1 in molar ratio fully, add and 3 again, 5-dinitrobenzoyl chloride molar ratio computing is 1.1 aluminum trichloride (anhydrous), at 25 ℃ of stirring reaction 1h, pour in mass concentration 15% dilute phosphoric acid solution, get II-1 intermediate 3 behind the separatory decompressing and extracting solvent, 5-dinitrobenzene-3 ', 4 '-dimethyl benzophenone; With mass concentration is that 40% nitric acid and II-1 intermediate added in the withstand voltage reactor of sealing in 4: 1 in molar ratio, at 120 ℃ of reaction 8h, be cooled to room temperature and filter, behind the washing and drying II-2 intermediate 3,5-dinitrobenzene-3 ', 4 '-dicarboxylic acid benzophenone; Will urea and the II-2 intermediate added in 1: 1 in molar ratio and make it dissolving among the DMAc fully, and at 120 ℃ of reaction 1h down, drain behind the solvent II-3 intermediate 4-(3,5-dinitrobenzene ketone) phthalic imidine; Ammoniacal liquor and II-3 intermediate were mixed in 4: 1 in molar ratio,, get II-4 intermediate 4-(3,5-dinitrobenzene ketone) phthalic diamide behind the filtration drying at 25 ℃ of reaction 5h; To be that 40: 1 sulfur oxychloride slowly is added dropwise in the cooled DMF of ice-water bath (consumption will make the II-4 dissolving fully) with II-4 intermediate mol ratio earlier, again the II-4 intermediate is added wherein, then at 30 ℃ of reaction 2h, pour in the big water gaging and precipitate, get II-5 intermediate 4-(3,5-dinitrobenzene ketone) phthalonitrile behind the filtration drying; 1gII-5 intermediate, 5ml DMF are added in the reactor, under nitrogen atmosphere, add and count 0.5% Pd/C (concentration 10%), react 8h down at 40 ℃ then, filter, drain solvent and get product monomer 4 with II-5 intermediate quality.
FTIR (the cm of the monomer that obtains 4
-1): 3459,3376 (N-H), 3080 (C=C-H), 2230 (CN), 1650 (C=O).
1H?NMR(DMSO-d
6ppm)：8.10-8.20(d，1H，Ar-H)，7.70-7.72(d，1H，Ar-H)，7.20-7.30(dd，1H，Ar-H)，7.02(dd，1H，Ar-H)，6.28-6.30(dd，2H，Ar-H)，5.2(s，4H，NH
2)。Ultimate analysis calculated value: C, 68.69; H, 3.84; N, 21.36; O, 6.10 element measured value: C, 68.71; H, 3.81; N:21.34; O, 6.14.
Adding monomer 4 in polar solvent NMP is stirred to it and dissolves fully, adding and monomer 4 mol ratios are 3: 3 aromatic dianhydride compd B TPA again, adding and monomer 4 mol ratios are phthalic anhydride/pyridine of 10: 1 behind the stirring at room 4h, react 4h down at 80 ℃, reaction solution is poured in the water, promptly get the polyimide of phthalonitrile pendant group after the separation drying, the η that records
Imh=1.9dL/g, Mn=102000.
After adding monomer 4 is stirred to dissolving fully in polar solvent NMP, add mol ratio with monomer 4 again and be 3: 1 acid binding agent oxyethane and with monomer 4 mol ratios be 3: 3 fragrant diacid chloride compd B PDC, after-10 ℃ are stirred 12h down, reaction solution is poured in the precipitation agent methanol, get the polymeric amide of phthalonitrile pendant group after the separation drying, the η that records
Inh=2.0dL/g, Mn=110700.
Embodiment 5
Present embodiment is monomer 4 synthetic in the II class monomer.
Earlier with o-Xylol and 3, the 5-dinitrobenzoyl chloride was dissolved in the o-Xylol in 1: 0.9 in molar ratio fully, add and 3 again, 5-dinitrobenzoyl chloride molar ratio computing is 3 aluminum trichloride (anhydrous), at 10 ℃ of stirring reaction 3h, pour in mass concentration 20% dilute hydrochloric acid solution, get II-1 intermediate 3 behind the separatory decompressing and extracting solvent, 5-dinitrobenzene-3 ', 4 '-dimethyl benzophenone; With mass concentration is that 30% nitric acid and II-1 intermediate added in the withstand voltage reactor of sealing in 16: 1 in molar ratio, at 150 ℃ of reaction 6h, be cooled to room temperature and filter, behind the washing and drying II-2 intermediate 3,5-dinitrobenzene-3 ', 4 '-dicarboxylic acid benzophenone; Will urea and the II-2 intermediate added in 4: 1 in molar ratio and make it dissolving among the DMF fully, and at 140 ℃ of reaction 2h down, drain behind the solvent II-3 intermediate 4-(3,5-dinitrobenzene ketone) phthalic imidine; Ammoniacal liquor and II-3 intermediate were mixed in 12: 1 in molar ratio,, get II-4 intermediate 4-(3,5-dinitrobenzene ketone) phthalic diamide behind the filtration drying at 15 ℃ of reaction 10h; To be that 20: 1 sulfur oxychloride slowly is added dropwise in the cooled DMF of ice-water bath (consumption will make the II-4 dissolving fully) with II-4 intermediate mol ratio earlier, again the II-4 intermediate is added wherein, then at 20 ℃ of reaction 4h, pour in the big water gaging and precipitate, get II-5 intermediate 4-(3,5-dinitrobenzene ketone) phthalonitrile behind the filtration drying; 1g II-5 intermediate, 200ml dehydrated alcohol are added in the reactor, under nitrogen atmosphere, add and count 10% Pd/C (concentration 5%), react 4h down at 80 ℃ then, filter, drain solvent and get product monomer 4 with II-5 intermediate quality.
Embodiment 6
Present embodiment is monomer 5 synthetic in the II class monomer and prepares the embodiment of polyimide and polymeric amide respectively with it.
Earlier with o-Xylol and 4,4 '-dinitrobenzene-2,2 '-dimethyl chloride biphenyl was dissolved in 1 in 3: 1 in molar ratio fully, in the 2-ethylene dichloride, add and 3 again, 5-dinitrobenzoyl chloride molar ratio computing is 4: 1 an anhydrous tri-chlorination zinc, at 35 ℃ of stirring reaction 4.5h, pours in mass concentration 10% dilution heat of sulfuric acid, get II-1 intermediate 4 behind the separatory decompressing and extracting solvent, 4 '-dinitrobenzene-2,2 '-(3,4-dimethyl benzene ketone) biphenyl; With mass concentration is that 50% nitric acid and II-1 intermediate added in the withstand voltage reactor of sealing in 25: 1 in molar ratio, at 160 ℃ of reaction 4h, is cooled to room temperature and filters, get II-2 intermediate 4 behind the washing and drying, 4 '-dinitrobenzene-2,2 '-(3,4-dicarboxyl benzophenone) biphenyl; Will urea and the II-2 intermediate added in 8: 1 in molar ratio and make it dissolving among the DMSO fully, and at 150 ℃ of reaction 3h down, behind the decompressing and extracting solvent II-3 intermediate 4,4 '-dinitrobenzene-2,2 '-(3,4-dicarboximide benzophenone) biphenyl; Earlier the II-3 intermediate is dissolved in the methyl alcohol, and continues to feed ammonia and stir the 20h after-filtration, get II-4 intermediate 4,4 '-dinitrobenzene-2,2 '-(3,4-diformamide benzophenone) biphenyl after the drying at 25 ℃; Earlier with 4,4 '-dinitrobenzene-2,2 '-(3,4-diformamide benzophenone) biphenyl is dissolved in N, in the N-two first class aniline solvents, drip mol ratio again and be 2: 1 dewatering agent phosphorus oxychloride, at 70 ℃ of reaction 8h, pour in the big water gaging and precipitate then, get II-5 intermediate 4 behind the filtration drying, 4 '-dinitrobenzene-2,2 '-(3,4-dicyanobenzenes ketone) biphenyl; 1g II-5 intermediate, 100mlTHF are added in the reactor, under nitrogen atmosphere, add and count 5% Pd/C (concentration 5%), at room temperature react 24h then, filter, drain solvent and get product monomer 5 with II-5 intermediate quality.
FTIR (the cm of the monomer that obtains 5
-1): 3455,3373 (N-H), 3060 (C=C-H), 2233 (CN), 1652 (C=O).
1H?NMR(DMSO-d
6ppm)：8.30-8.35(d，4H，Ar-H)，8.10-8.12(d，2H，Ar-H)，7.80-7.89(d，2H，Ar-H)，6.25-6.28(d，2H，Ar-H)，6.18-6.20(dd，2H，Ar-H)，5.3(s，4H，NH
2)。Ultimate analysis calculated value: C, 73.16; H, 3.27; N, 17.06; O, 6.50 element measured value: C, 73.18; H, 3.21; N:17.00; O, 6.61.
Adding monomer 5 in polar solvent DMF is stirred to it and dissolves fully, add aromatic dianhydride compound F 17-hydroxy-corticosterone DA again with mol ratios such as monomer 5, adding and monomer 5 mol ratios are 15: 1 dimethylbenzene behind the stirring at room 24h, react 6h down at 150 ℃, reaction solution is poured in the ethanol, promptly get the polyimide of phthalonitrile pendant group after the separation drying, the η that records
Inh=2.0dL/g, Mn=119000.
After adding monomer 5 is stirred to dissolving fully in polar solvent NMP, add mol ratio with monomer 5 again and be 4: 1 the acid binding agent triethylamine and with the fragrant diacid chloride compound ODC of mol ratio such as monomer 5, after 20 ℃ are stirred 20h down, reaction solution is poured in the precipitation agent ethanol, get the polymeric amide of phthalonitrile pendant group after the separation drying, the η that records
Inh=2.0dL/g, Mn=117000.
Embodiment 7
Present embodiment is monomer 5 synthetic in the II class monomer.
Earlier with o-Xylol and 4,4 '-dinitrobenzene-2,2 '-dimethyl chloride biphenyl was dissolved in the dithiocarbonic anhydride in 4.2: 1 in molar ratio fully, and adding and 3,5 dinitrobenzoylchloride molar ratio computing are 8: 1 anhydrous tri-chlorination zinc again, at 50 ℃ of stirring reaction 6h, pour in mass concentration 3% dilute hydrochloric acid solution, get II-1 intermediate 4,4 '-dinitrobenzene-2 behind the separatory decompressing and extracting solvent, 2 '-(3,4-dimethyl benzene ketone) biphenyl; With mass concentration is that 60% nitric acid and II-1 intermediate added in the withstand voltage reactor of sealing in 50: 1 in molar ratio, at 180 ℃ of reaction 2h, is cooled to room temperature and filters, get II-2 intermediate 4 behind the washing and drying, 4 '-dinitrobenzene-2,2 '-(3,4-dicarboxyl benzophenone) biphenyl; Will urea and the II-2 intermediate added in 16: 1 in molar ratio and make it dissolving among the NMP fully, and at 160 ℃ of reaction 0.5h down, behind the decompressing and extracting solvent II-3 intermediate 4,4 '-dinitrobenzene-2,2 '-(3,4-dicarboximide benzophenone) biphenyl; The II-3 intermediate that will be 1: 35 earlier in molar ratio is dissolved in the ethylene glycol, and continues to feed ammonia and stir the 1h after-filtration at 80 ℃, gets II-4 intermediate 4,4 '-dinitrobenzene-2,2 '-(3,4-diformamide benzophenone) biphenyl after the drying; Earlier with 4,4 '-dinitrobenzene-2,2 '-(3,4-diformamide benzophenone) biphenyl is dissolved in N, in the accelerine solvent, drip mol ratio again and be 8: 1 dewatering agent phosphorus oxychloride, at 70 ℃ of reaction 10h, pour in the big water gaging and precipitate then, get II-5 intermediate 4 behind the filtration drying, 4 '-dinitrobenzene-2,2 '-(3,4-dicyanobenzenes ketone) biphenyl; 1g II-5 intermediate, 20ml acetone are added in the reactor, under nitrogen atmosphere, add and count 1% Pd/C (concentration 10%), at room temperature react 48h then, filter, drain solvent and get product monomer 5 with II-5 intermediate quality.
Embodiment 8
Present embodiment is monomer 6-1 synthetic in the III class monomer and prepares the embodiment of polyimide and polymeric amide respectively with it.
Earlier will be with 3,5-dinitrobenzoyl chloride molar ratio computing is that 1: 0.9 4-(4-hydroxyphenoxy) phthalonitrile adds among the THF it is dissolved fully, add and 3 again, 5-dinitrobenzoyl chloride molar ratio computing is 1: 0.9 an acid binding agent pyridine, add 3,5 dinitrobenzoylchloride at last, and at 20 ℃ of following stirring reaction 12h, pour into again in the big water gaging and precipitate, get product III-1 after the separation drying; To in the 1gIII-1 intermediate adding 20ml dehydrated alcohol it be dissolved fully, and adding be counted 0.5% Pd/C (concentration 10%) with III-1 intermediate quality under nitrogen atmosphere, at room temperature reacts 48h, filters, and drains solvent and gets product monomer 6-1.
FTIR (the cm of gained monomer 6-1
-1): 3411,3336 (N-H), 2231 (CN), 1727,1702 (C=O), 1203 (C-O-C).
1H?NMR(DMSO-d
6ppm)：8.12-8.15(d，1H，Ar-H)，7.90-7.98(d，1H，Ar-H)，7.32-7.36(dd，1H，Ar-H)，7.24-7.35(dd，2H，Ar-H)，7.05-7.16(dd，2H，Ar-H)，6.30-6.35(dd，2H，Ar-H)，6.22-6.25(m，1H，Ar-H)，5.0(s，4H，NH
2)。Ultimate analysis calculated value: C, 68.10; H, 3.81; N, 15.13; O, 12.96 element measured value: C, 68.12; H, 3.89; N:15.20; O, 12.79.
Adding monomer 6-1 in polar solvent DMAc is stirred to it and dissolves fully, add aromatic dianhydride compound S DPA again with mol ratios such as monomer 6-1, adding and monomer 6-1 mol ratio are 20: 1 N behind the stirring at room 10h, N di-n-butyl aniline, react 20h down at 140 ℃, reaction solution is poured in the water, promptly got the polyimide of phthalonitrile pendant group after the separation drying, the η that records
Inh=1.7dL/g, Mn=99400.
After adding monomer 6-1 is stirred to dissolving fully in polar solvent DMAc, add mol ratio with monomer 6-1 again and be 2: 1 acid binding agent oxyethane and with the fragrant diacid chloride compound S DC of mol ratio such as monomer 6-1, after 10 ℃ are stirred 18h down, reaction solution is poured in the precipitation agent water, get the polymeric amide of phthalonitrile pendant group after the separation drying, the η that records
Inh=1.5dL/g, Mn=90800.
Embodiment 9
Present embodiment is monomer 6-2 synthetic in the III class monomer and prepares the embodiment of polyimide and polymeric amide respectively with it.
Earlier will be with 3,5-dinitrobenzoyl chloride molar ratio computing is that 1: 1.2 4-(4-xenol oxygen base) phthalonitrile adds in the acetone it is dissolved fully, add and 3 again, 5-dinitrobenzoyl chloride molar ratio computing is 1: 1.2 an acid binding agent triethylamine, add 3,5 dinitrobenzoylchloride at last, and at 10 ℃ of following stirring reaction 48h, pour into again in the big water gaging and precipitate, get product III-1 after the separation drying; To among the 1gIII-1 intermediate adding 20ml THF it be dissolved fully, and adding be counted 10% Pd/C (concentration 5%) with III-1 intermediate quality under nitrogen atmosphere, reacts 4h down at 80 ℃, filters, and drains solvent and gets product monomer 6-2.
FTIR (the cm of gained monomer 6-2
-1): 3412,3335 (N-H), 2232 (CN), 1732,1706 (C=O), 1206 (C-O-C).
1H?NMR(DMSO-d
6ppm)：8.10-8.13(d，1H，Ar-H)，7.94-7.96(d，1H，Ar-H)，7.34-7.40(dd，1H，Ar-H)，7.30-7.35(m，4H，Ar-H)，7.10-7.16(m，4H，Ar-H)，6.32-6.36(dd，2H，Ar-H)，6.21-6.24(m，1H，Ar-H)，5.1(s，4H，NH
2)。Ultimate analysis calculated value: C, 72.64; H, 4.06; N, 12.55; O, 10.75 element measured value: C, 72.60; H, 4.01; N:12.50; O, 10.89.
Adding monomer 6-2 in polar solvent DMSO is stirred to it and dissolves fully, add aromatic dianhydride compd B PDA again with mol ratios such as monomer 6-2, adding and monomer 6-2 mol ratio are trifluoroacetic anhydride/triethylamine (volume ratio 1: 1) of 6: 1 behind the stirring at room 20h, react 6h down at 40 ℃, reaction solution is poured in the methyl alcohol, promptly get the polyimide of phthalonitrile pendant group after the separation drying, the η that records
Inh=0.23dL/g, Mn=5100.
After adding monomer 6-2 is stirred to dissolving fully in polar solvent DMSO, add mol ratio with monomer 6-2 again and be 4: 1 the acid binding agent pyridine and with the fragrant diacid chloride Compound I PC of mol ratio such as monomer 6-2, after 0 ℃ is stirred 22h down, reaction solution is poured in the precipitation agent methanol, get the polymeric amide of phthalonitrile pendant group after the separation drying, the η that records
Inh=0.21dL/g, Mn=5300.
Embodiment 10
Present embodiment is monomer 7 synthetic in the III class monomer and prepares the embodiment of polyimide and polymeric amide respectively with it.
Earlier will be with 3,5-dinitrobenzoyl chloride molar ratio computing is that 1: 1.5 4-hydroxyl phthalonitrile adds among the DMF it is dissolved fully, add and 3 again, 5-dinitrobenzoyl chloride molar ratio computing is 1: 1.5 an acid binding agent propylene oxide, add 3,5 dinitrobenzoylchloride at last, and at 40 ℃ of following stirring reaction 4h, pour into again in the big water gaging and precipitate, get product III-1 after the separation drying; To among the 1gIII-1 intermediate adding 10ml DMF it be dissolved fully, and adding be counted 5% Pd/C (concentration 5%) with III-1 intermediate quality under nitrogen atmosphere, reacts 24h down at 40 ℃, filters, and drains solvent and gets product monomer 7.
FTIR (the cm of gained monomer 7
-1): 3409,3330 (N-H), 2233 (CN), 1735,1712 (C=O), 1210 (C-O-C).
1H?NMR(DMSO-d
6ppm)：8.12-8.15(d，1H，Ar-H)，7.97-8.01(d，1H，Ar-H)，7.40-7.43(dd，1H，Ar-H)，6.42-6.46(dd，2H，Ar-H)，6.31-6.34(m，1H，Ar-H)，5.3(s，4H，NH
2)。Ultimate analysis calculated value: C, 64.74; H, 3.62; N, 20.13; O, 11.50 element measured value: C, 64.70; H, 3.61; N:20.20; O, 11.49.
Adding monomer 7 in polar solvent NMP is stirred to it and dissolves fully, add aromatic dianhydride compound ODPA again with mol ratios such as monomer 7, adding and monomer 7 mol ratios are 7: 1 DCC behind the stirring at room 6h, at room temperature react 12h, reaction solution is poured in the water, promptly get the polyimide of phthalonitrile pendant group after the separation drying, the η that records
Inh=0.64dL/g, Mn=54100.
After adding monomer 7 is stirred to dissolving fully in polar solvent NMP, add mol ratio with monomer 7 again and be 2: 1 the acid binding agent triethylamine and with the fragrant diacid chloride compd B PDC of mol ratio such as monomer 7, after-5 ℃ are stirred 16h down, reaction solution is poured in the precipitation agent water, get the polymeric amide of phthalonitrile pendant group after the separation drying, the η that records
Inh=0.58dL/g, Mn=47200.
Claims (8)
1, the aromatic diamine of phthalonitrile pendant group, the general structure of this aromatic diamine is:
2, the aromatic diamine of phthalonitrile pendant group according to claim 1, this aromatic diamine are any in following general structure I, II, the III class monomer:
I class monomer
II class monomer
III class monomer
3, a kind of method for preparing the aromatic diamine of the described phthalonitrile pendant group of claim 2, wherein the reaction equation of the monomer 3 in I class monomer and the II class monomer, preparation method's processing step and condition are as follows:
Earlier component A and 4 (3)-nitrophthalonitriles are calculated in molar ratio as 0.3-1.2: 1 is dissolved in the solvent orange 2 A fully, adding with 4-nitrophthalonitrile molar ratio computing again is the catalyst A of 1-3, and at the room temperature-160 ℃ following 4-24h that stirs, decompressing and extracting solvent orange 2 A then, washing promptly gets intermediate compound I-1 after the separation drying; Obtaining I-1 intermediate and solvent B are added in the reactor, under nitrogen atmosphere, add the catalyst B of counting 0.5-10% by the quality of intermediate compound I-1,, filter, drain solvent B and get product I-2 at room temperature-80 ℃ reaction 8-48h;
The reaction equation of the monomer 4,5 in the II class monomer, preparation method's processing step and condition are as follows:
Earlier with o-Xylol and B component 0.9-4.2 in molar ratio: 1 is dissolved in the solvent C fully, add with the molar ratio computing of B component is the catalyzer C of 1.1-8 again, at 10-50 ℃ of reaction 1-6h, to pour in the dilute acid soln of mass concentration＜20%, filtration or separatory get the II-1 intermediate after draining solvent C; With mass concentration is the nitric acid of 30-60% and II-1 intermediate 4-50 in molar ratio: 1 adds in the withstand voltage reactor of sealing, at 120-180 ℃ of reaction 2-8h, filter behind the washing and drying the II-2 intermediate; With urea and II-2 intermediate 1-16 in molar ratio: 1 adds and makes it dissolving among the solvent D fully, and at 120-160 ℃ of reaction 0.5-4h down, drain behind the solvent D the II-3 intermediate; With amidation reagent and II-3 intermediate 4-35 in molar ratio: 1 mixes, or the II-3 intermediate is dissolved in feeds amidation reagent among the solvent E more earlier, at 15-80 ℃ of reaction 1-20h, behind the filtration drying the II-4 intermediate; The II-4 intermediate is dissolved among the solvent F fully, adding with II-4 intermediate mol ratio is 2-40 again: 1 dewatering agent or will be 2-40 with II-4 intermediate mol ratio earlier: 1 dewatering agent mixes with solvent F, solvent F consumption will make the II-4 dissolving fully, again the II-4 intermediate is added wherein, behind 20-90 ℃ of reaction 2-10h, pour in the big water gaging then and precipitate, get the II-5 intermediate behind the filtration drying; The solid content 0.5-20% (g/ml) that II-5 intermediate, solvent G is pressed II-5 adds in the reactor, under nitrogen atmosphere, add the catalyzer D that counts 0.5-10% with II-5 intermediate quality, at room temperature-80 ℃ following reaction 4-48h, filter then, drain solvent G and get product II-6;
The monomeric reaction equation of III class, preparation method's processing step and condition are as follows:
Earlier will be with 3,5-dinitrobenzoyl chloride molar ratio computing is 1: the component C of 0.9-1.5 adds among the solvent H dissolves it fully, add and 3 again, 5-dinitrobenzoyl chloride molar ratio computing is 1: the acid binding agent of 0.9-1.5, add 3,5 dinitrobenzoylchloride at last, and at 10-40 ℃ of following stirring reaction 4-24h, pour into again in the big water gaging and precipitate, get product III-1 after the separation drying; Will the III-1 intermediate add among the solvent I it will be dissolved fully, and under nitrogen atmosphere, add the catalyzer E that counts 0.5-10% with III-1 intermediate quality,, filter, drain solvent I and get product III-2 at ℃ following reaction 4-48h of room temperature-80.
4, the preparation method of the aromatic diamine of phthalonitrile pendant group according to claim 3, this method prepare 3 among the used component A of I class monomer, and 5-dinitrobenzene-4 '-dihydroxy benaophenonel prepares by following synthesis technique:
Earlier with 3,5-dinitrobenzoyl chloride and methyl-phenoxide or phenyl ethyl ether be 0.9-1.2 in molar ratio: 1 is dissolved among the solvent J fully, adding and methyl-phenoxide or phenyl ethyl ether molar ratio computing are the catalyzer F of 1.1-4 again, and at 10-50 ℃ of following reaction 2-6h, pour into then in mass concentration＜20% dilute acid soln, filtration or separatory get product after draining solvent.
5, the preparation method of the aromatic diamine of phthalonitrile pendant group according to claim 4, used solvent J is benzene second (first) ether, methylene dichloride, 1 in this method, any in 2-ethylene dichloride, the dithiocarbonic anhydride; Used catalyzer F is any in aluminum trichloride (anhydrous), anhydrous tri-chlorination zinc, the FERRIC CHLORIDE ANHYDROUS; Dilute acid soln is any in dilute hydrochloric acid, dilute sulphuric acid, the dilute phosphoric acid.
6, the preparation method of the aromatic diamine of phthalonitrile pendant group according to claim 3, used solvent orange 2 A is N in this method, in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO) or the N-Methyl pyrrolidone (NMP) any; Solvent B is any in dehydrated alcohol, DMF, tetrahydrofuran (THF) (THF), ethyl acetate or the acetone; Solvent C is o-Xylol, methylene dichloride, 1, any in 2-ethylene dichloride or the dithiocarbonic anhydride; Solvent D is N, any among dinethylformamide DMF, N,N-dimethylacetamide DMAc, dimethyl sulfoxide (DMSO) DMSO or the N-Methyl pyrrolidone NMP; Solvent E is methyl alcohol, ethylene glycol, N, any among the dinethylformamide DMF; Solvent F is DMF or N, accelerine; Solvent G dehydrated alcohol, N, any in dinethylformamide DMF, tetrahydrofuran THF, ethyl acetate (EA), the acetone;
Used catalyst A is Anhydrous potassium carbonate or anhydrous sodium carbonate in this method; It is 10% or 5%Pd/C that catalyst B, D and E are massfraction; Catalyzer C is any in aluminum trichloride (anhydrous), anhydrous tri-chlorination zinc or the FERRIC CHLORIDE ANHYDROUS;
Used amidation reagent is strong aqua or ammonia in this method; Used dilute acid soln is any in dilute hydrochloric acid, dilute sulphuric acid or the dilute phosphoric acid; Used dewatering agent is thionyl chloride or phosphorus oxychloride; Used acid binding agent is any in pyridine, triethylamine, propylene oxide or the 4-Dimethylamino pyridine (DMAP).
7, the polyimide of phthalonitrile pendant group, this polyimide are to be formed by the aromatic diamine of phthalonitrile pendant group and aromatic dianhydride compound, and the structural formula that its reaction generates is as follows:
Or
Wherein used aromatic dianhydride compound is equal benzene four acid anhydrides, phenyl ether dianhydride, biphenyl dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4-(hexafluoro sec.-propyl) diphthalic anhydrides, 3,3 ', 4, any in 4 '-diphenylsulfone acid dianhydride, n=8-200, the intrinsic viscosity of this polyimide is 0.2-2.0dL/g, and number-average molecular weight is 5000-120000g/mol.
8, the polymeric amide of phthalonitrile pendant group, this polymeric amide are to be formed by the aromatic diamine of phthalonitrile pendant group and diacid chloride compound, and the structural formula that its reaction generates is as follows:
Or
Wherein used fragrant diacid chloride compound is p-phthaloyl chloride, m-phthaloyl chloride, 2, in 6-naphthalene dimethyl chloride, biphenyl dimethyl chloride, phenyl ether dimethyl chloride, the sulfobenzide dimethyl chloride any, n=9-200, the intrinsic viscosity of this polymeric amide is 0.2-2.0dL/g, and number-average molecular weight is 5000-120000g/mol.
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| CN101143928B (en) * | 2007-09-12 | 2010-09-08 | 四川大学 | Poly-o-phthalonitrile resin and its preparing process |
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