CN103012790B - Bisphthalonitrile-amino phenoxy phthalonitrile copolymer and condensate, and glass fiber composite material and preparation method thereof - Google Patents
Bisphthalonitrile-amino phenoxy phthalonitrile copolymer and condensate, and glass fiber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high molecular materials, in particular relates to a bisphthalonitrile-amino phenoxy phthalonitrile copolymer and condensate as well as a glass fiber composite material and a preparation method thereof. The bisphthalonitrile-amino phenoxy phthalonitrile copolymer, provided by the invention, is obtained by fusing and copolymerizing bisphthalonitrile and amino phenoxy phthalonitrile at the temperature of 200-220 DEG C. The method adopts the amino phenoxy phthalonitrile with low cost to obtain the bisphthalonitrile-amino phenoxy phthalonitrile copolymer and the condensate; and the obtained condensate has excellent flame retardance (oxygen index is more than 36 percent); the bending strength achieves 88-130 MPa; the original decomposition temperature is above 478 DEG C; and the carbon residue rate at the temperature of 800 DEG C is more than 65 percent.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer, cured article and glass fiber composite material and preparation method.
Background technology
Bi-phthalonitrile resin is to be synthesized at first by the Keller seminar of US Naval Research Laboratory, be a kind of high-performance high temperature resistant thermosetting resin its there is excellent thermostability and thermo-oxidative stability, good mechanical property and higher moistureproofness etc., there is the functional characteristicss such as anticorrosive, resistance to irradiation, high strength; It is obtained a wide range of applications in fields such as aerospace, naval vessel, machinery, electronics, and can prepare functional high molecule material, paint/coating, polymer matrix composites, high temperature resistant binder, electronic conductor, semi-conductor, organic magnetic functional materials.It is the high-performance thermosetting resin based on phthalonitrile that the first has bibliographical information.Under heating condition, bis-phthalonitrile monomer forms bi-phthalonitrile resin by the polyaddition reaction of itrile group.From 20 century 70s, systematic research has been carried out in the aspects such as preparation, processing, performance and the application of Keller seminar to bi-phthalonitrile, has obtained some valuable results at synthetic, processing and the aspect of performance of monomer.After this, the matrix material that they propose taking this resin as matrix is the resistance to elevated temperatures matrix material that has great development potentiality.
Applicant of the present invention has also carried out a large amount of research for o-phthalonitrile resin, and has Patents bibliographical information, as ZL2006100213342 " double-terminal phthalonitrile resin, cured article and its production and use "; ZL2008103065093 " magnetic ferrocene-double-terminal phthalonitrile resin, cured article and their preparation method ".
But, the shortcoming such as it is high that bi-phthalonitrile has processing temperature simultaneously, and curing reaction is slow, thus limit its application; For example: the fusing point of biphenyl type phthalonitrile is 247 DEG C, the in the situation that of catalyst-free, solidify hardly; The fusing point of bisphenol A-type phthalonitrile is 197 DEG C, the in the situation that of catalyst-free, solidifies hardly.So " containing the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments, cured article and preparation method thereof " that application number is 2010102272271 synthesized the lower bi-phthalonitrile resin of processing temperature for its shortcoming, but synthesis step trouble.Also have pertinent literature to reduce the processing temperature of bi-phthalonitrile by adding the resins such as epoxy, still, the consistency of bi-phthalonitrile and epoxy is poor, and result shows that the interpolation of epoxy has damaged the heat-proof combustion-resistant performance of bi-phthalonitrile.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer, and it is that bi-phthalonitrile and amino-benzene oxygen phthalonitrile are obtained in 200 ~ 220 DEG C of melting copolymerization.
Above-mentioned bi-phthalonitrile is biphenyl type bi-phthalonitrile or bisphenol A-type bi-phthalonitrile.
The present invention also provides the preparation method of above-mentioned bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer, the melting copolymer-1 0-40min at 200-220 DEG C by bi-phthalonitrile and amino-benzene oxygen phthalonitrile, obtains bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer.
Preferably, the preparation method of above-mentioned bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer: bi-phthalonitrile is stirred after melting at 200 DEG C-220 DEG C, continue to stir 5-10min, progressively add again amino-benzene oxygen phthalonitrile to make its complete melting, then stir 10-30min and obtain bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer of the present invention.
Second technical problem to be solved by this invention is to provide a kind of bi-phthalonitrile-amino-benzene oxygen phthalonitrile cured article, its be by above-mentioned bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer pour into a mould, thermal treatment makes; Described heat-treat condition is to process 4-14h at 200-350 DEG C; Preferably, described thermal treatment adopts Fractional Heat-treatment, and heat-treat condition is: 200-220 DEG C/1-2h, and 230-250 DEG C/1-4h, 260-290 DEG C/1-4h, 300-350 DEG C/1-4h; Preferred, heat-treat condition is: 200 DEG C/2h, and 240 DEG C/2h, 280 DEG C/4h, 320 DEG C/4h.
Gained cured article oxygen index is greater than 36%, flexural strength 88～130MPa, and temperature of initial decomposition is more than 478 DEG C, 800 DEG C of carbon residue rates are greater than 65%.
The 3rd technical problem to be solved by this invention is to provide a kind of glass fibre reinforced composite material, it is taking above-mentioned bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer and glass as raw material, and the weight ratio of bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer and glass is: 30～50 ︰ 70～50.
Preferably, in above-mentioned bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer glass fibre reinforced composite material, the weight ratio of bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer and glass is 40:60.
Gained glass fibre reinforced composite material oxygen index is greater than 39%, and flexural strength reaches 525～710MPa, and temperature of initial decomposition is more than 500 DEG C, and 800 DEG C of carbon residue rates are greater than 80%.
Above-mentioned glass fibre reinforced composite material (glass strengthens the matrix material of bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer) adopts the dry legal preparation of wet mixing.
Four technical problems to be solved by this invention are to provide a kind of glass and strengthen composite solid compound, its be by above-mentioned glass fibre reinforced composite material pour into a mould, thermal treatment makes; Described heat-treat condition is to process 1-4h at 340-380 DEG C; Preferably, described heat-treat condition is: 340 DEG C/1-4h or 360 DEG C/1-4h or 380 DEG C/1-4h; Preferred, described heat-treat condition is: 340 DEG C/4h or 360 DEG C/4h or 380 DEG C/4h.
Gained glass strengthens composite solid compound flexural strength and reaches 701～723MPa, and temperature of initial decomposition is more than 589 DEG C.
Beneficial effect of the present invention:
First, the present invention adopts cheap amino-benzene oxygen phthalonitrile, obtain bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer and cured article, gained cured article has outstanding flame retardant properties (oxygen index is greater than 36%), flexural strength reaches 88～130MPa, temperature of initial decomposition is more than 478 DEG C, and 800 DEG C of carbon residue rates are greater than 65%.Secondly, the invention provides bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer/glass fiber composite material, gained glass fibre reinforced composite material has outstanding flame retardant properties (oxygen index is greater than 39%), flexural strength reaches 525～710MPa, temperature of initial decomposition is more than 500 DEG C, and 800 DEG C of carbon residue rates are greater than 80%.Matrix material performance after Overheating Treatment is better, and thermal treatment gained composite solid compound flexural strength reaches 701～723MPa, and temperature of initial decomposition is more than 589 DEG C.Resulting materials can be widely used in the high-tech sectors such as aviation matrix material, microelectronics, naval, Aeronautics and Astronautics.
In addition, cured article of the present invention adopts casting, and glass fiber composite material adopts compression molding, matches with current industrial equipments, is easy to realize, and is easy to control, and has heavy industrialization application prospect.
Embodiment
First technical problem to be solved by this invention is to provide a kind of bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer, and it is that bi-phthalonitrile and amino-benzene oxygen phthalonitrile are obtained in 200 ~ 220 DEG C of melting copolymerization.
Preferably, wherein, the weight ratio of bi-phthalonitrile and amino-benzene oxygen phthalonitrile is 10～90 ︰ 90～10.
Wherein, above-mentioned bi-phthalonitrile is biphenyl type bi-phthalonitrile or bisphenol A-type bi-phthalonitrile, and the structural formula of amino-benzene oxygen phthalonitrile is shown in formula I:
Formula I.
The present invention also provides the preparation method of above-mentioned bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer, the melting copolymer-1 0-40min at 200-220 DEG C by bi-phthalonitrile and amino-benzene oxygen phthalonitrile, obtains bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer; Wherein, the weight ratio of bi-phthalonitrile and amino-benzene oxygen phthalonitrile is 10～90 ︰ 90～10.
Preferably, the preparation method of above-mentioned bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer: bi-phthalonitrile is stirred after melting at 200 DEG C-220 DEG C, continue to stir 5-10min, make its abundant melting, progressively add again amino-benzene oxygen phthalonitrile to make its complete melting, then stir 10-30min, bi-phthalonitrile and amino-benzene oxygen phthalonitrile mixed and preliminary common prepolymerization reaction can occur, obtaining bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer.
Further, by the cooling rear abrasive dust of above-mentioned bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer, to be used for preparing batten and sheet material.
Second technical problem to be solved by this invention is to provide a kind of bi-phthalonitrile-amino-benzene oxygen phthalonitrile cured article, its be by above-mentioned bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer pour into a mould, thermal treatment makes; Gained cured article has oxygen index and is greater than 36%, flexural strength 88～130MPa, and temperature of initial decomposition is more than 478 DEG C, 800 DEG C of carbon residue rates are greater than 65%.
The 3rd technical problem to be solved by this invention is to provide a kind of glass fibre reinforced composite material, it is taking above-mentioned bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer and glass as raw material, and the weight ratio of bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer and glass is: 30～50 ︰ 50～70.Gained glass fibre reinforced composite material oxygen index is greater than 39%, and flexural strength reaches 525～710MPa, and temperature of initial decomposition is more than 500 DEG C, and 800 DEG C of carbon residue rates are greater than 80%.
When the present invention prepares glass fibre reinforced composite material, the existing method of preparing superpolymer/glass fiber composite material all can be used, as legal in dry method, wet method, dry wet mixing; Find through test, strengthen the matrix material of bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer for glass, dry legal dry method and the wet method of being better than of wet mixing.
Four technical problems to be solved by this invention are to provide a kind of glass and strengthen composite solid compound, its be by above-mentioned glass fibre reinforced composite material pour into a mould, thermal treatment makes; Gained glass strengthens composite solid compound flexural strength and reaches 701～723MPa, and temperature of initial decomposition is more than 589 DEG C.
The fusing point of the amino-benzene oxygen phthalonitrile that the present invention adopts is 145 DEG C (lower 100 DEG C than biphenyl type phthalonitrile, lower 50 DEG C than bisphenol A-type phthalonitrile), and amino-benzene oxygen phthalonitrile originally amino with it there is the effect of catalysis phthalonitrile curing reaction; The present invention is by the low melting point of amino-benzene oxygen phthalonitrile, high catalysis, and the consistency of the analog structure of bi-phthalonitrile itself,
Select bisphenol A-type phthalonitrile and the copolymerization of 3-amino-benzene oxygen phthalonitrile of relative low price, obtain bisphenol A-type phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer, multipolymer thermal treatment is obtained to bisphenol A-type phthalonitrile/3-amino-benzene oxygen phthalonitrile cured article, and apply it in glass fibre reinforced composite material field, study the preparation method of its best glass fibre reinforced composite material, provide the variation of thermal treatment front and back performances, develop a kind of high strength, high-modulus, high temperature resistant, Halogen is from the bisphenol A-type phthalonitrile/3-of flame-retardant comprehensive excellent performance amino-benzene oxygen phthalonitrile cured article and glass fiber composite material.
By the mode of specific embodiment, the present invention is further described below, but should not be understood as limitation of the present invention, all amendments of making based on the above-mentioned thought of the present invention, replacement, change all belong to the present invention.In the embodiment of the present invention, all adopt bisphenol A-type phthalonitrile, but realizing object of the present invention is not limited to only use this type of bi-phthalonitrile, all types of bi-phthalonitriles all can adopt; Amino-benzene oxygen phthalonitrile used is 3-amino-benzene oxygen phthalonitrile.
Embodiment 1-5 bisphenol A-type bi-phthalonitrile-amino-benzene oxygen O-phthalic lonitrile copolymer and preparation thereof
Bisphenol A-type bi-phthalonitrile is placed in to beaker, stir after abundant melting at 200 DEG C-220 DEG C, continue to stir 5-10min, slowly add afterwards 3-amino-benzene oxygen phthalonitrile, then stir 10-30min, obtain bottle-green melt liquid, treat its cool to room temperature, broken into powder, obtained the powder of bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer.The properties of the different proportioning 3-of gained amino-benzene oxygen phthalonitrile/bisphenol A-type bi-phthalonitrile copolymer powder is as shown in table 1:
The performance of table 1 bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer
Embodiment 6-10 bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile cured article and preparation thereof
Get embodiment 1-5 gained bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile copolymer powder, stir abundant melting at 150-200 DEG C, after 5-10min, pour into a mould heat-treating profiled bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile cured article that makes; Wherein, heat treated temperature is 200 DEG C/2h, 240 DEG C/2h, and 280 DEG C/4h, 320 DEG C/4h; Flame retardant properties and the resistance toheat of gained cured article are as shown in table 2:
The performance of table 2 bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile cured article
Embodiment 11-17 bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile glass fiber composite material and preparation thereof
In order to prepare bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile glass fiber composite material of excellent combination property, we adopt three kinds of techniques: (1) dry method; (2) wet method; (3) dry wet mixing is legal, the multipolymer of choosing embodiment 3 gained adds glass-fibre for composite sheet (weight proportion of bisphenol A-type bi-phthalonitrile and 3-amino-benzene oxygen phthalonitrile is 50 ︰ 50), wherein, glass quality accounts for 62.5 parts, the quality of bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile copolymer powder accounts for 37.5 parts, and in three kinds of techniques, the weight proportion of bisphenol A-type bi-phthalonitrile and 3-amino-benzene oxygen phthalonitrile is 50 ︰ 50; Specific as follows:
1. dry method (embodiment 11):
(1) get the raw materials ready: 114 grams of glasscloths (20 layers, 20cm × 20cm); Bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile copolymer powder 68.4g;
(2) preparation process: a. dusting: see through two-layer gauze, uniformly bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile copolymer powder is spread on glasscloth to approximately 3.6～3.7 grams of powders on every glasscloth; B. dry cloth: by having spread 20 layers of glasscloth stack of powder, be placed in baking oven, dry cloth 3-5min in 180 DEG C; C. calendering: the glass-fiber-fabric that baking cloth is completed is placed in the grinding tool that scribbles releasing agent, compression moulding on hydropress; Pressing process is as follows: after placing several minutes at 200 DEG C, add 5MPa pressure, then relief pressure, three times repeatedly, is adjusted to 10MPa by pressure subsequently, repeatedly discharge three times, to get rid of air and the solvent in prepreg interlayer, then apply pressure to 15MPa, suppress according to following program: 200 DEG C/4h, 220 DEG C/2h, 250 DEG C/4h, 280 DEG C/4h, 320/4h.
2. wet method (embodiment 12):
(1) get the raw materials ready: 114 grams of glasscloths (20 layers, 20cm × 20cm); Bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile copolymer powder 68.4g; DMF 70ml;
(2) preparation process: a. joins glue: bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile copolymer powder of 68.4g is placed in to there-necked flask, adds 70mlN, N-METHYLFORMAMIDE, heated and stirred 1h, obtains bottle-green colloid; B. soak cloth: gained colloid is placed in to pallet, the glasscloth of handling well is dipped in above-mentioned colloid simultaneously; In layer the glasscloth having soaked is at room temperature hung to 24h, make solvent evaporates; C. dry cloth: the prepreg spending the night is placed in to baking oven, dries cloth 3-5min in 180 DEG C; D. calendering: the glass-fiber-fabric that baking cloth is completed is placed in the grinding tool that scribbles releasing agent, compression moulding on hydropress; Pressing process is as follows: after placing several minutes at 200 DEG C, add 5MPa pressure, then relief pressure, three times repeatedly, is adjusted to 10MPa by pressure subsequently, repeatedly discharge three times, to get rid of air and the solvent in prepreg interlayer, then apply pressure to 15MPa, suppress according to following program: 200 DEG C/4h, 220 DEG C/2h, 250 DEG C/4h, 280 DEG C/4h, 320/4h.
3. dry wet mixing legal (embodiment 13):
(1) get the raw materials ready: 114 grams of glasscloths (20 layers, 20cm × 20cm); Bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile copolymer powder 68.4g; N, N-METHYLFORMAMIDE 70ml;
(2) preparation process: a. joins glue: bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen phthalonitrile copolymer powder of 34.2g is placed in to there-necked flask, adds 70mLN, dinethylformamide, heated and stirred 1h, obtains bottle-green colloid; B. soak cloth: gained colloid is placed in to pallet, 20 layers of glasscloth handling well is dipped in colloid simultaneously, in layer glass fibre/colloid the prepreg having soaked is at room temperature hung to 24h, make solvent evaporates; C. dry cloth: the preimpregnation glass-fiber-fabric spending the night is placed in to baking oven, dries cloth 3-5min in 180 DEG C; D. dusting: see through two-layer gauze, uniformly powder is spread on woven fiber glass to approximately 1.8～1.9 grams of powders on every woven fiber glass; E. dry cloth: by having spread 20 layers of glasscloth stack of powder, be placed in baking oven, dry cloth 3-5min in 180 DEG C; F. calendering: the glass-fiber-fabric that has dried cloth is placed in to the grinding tool that scribbles releasing agent, compression moulding on hydropress; Pressing process is as follows: after placing several minutes at 200 DEG C, add 5MPa pressure, then relief pressure, three times repeatedly; Subsequently pressure is adjusted to 10MPa, repeatedly discharges three times, to get rid of air and the solvent in prepreg interlayer, then apply pressure to 15MPa, suppress according to following program: 200 DEG C/4h, 220 DEG C/2h, 250 DEG C/4h, 280 DEG C/4h, 320/4h.
Adopt the performance of bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer-glass fiber composite board material that above-mentioned three kinds of methods make as shown in table 3:
The performance of table 3 bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer-glass fiber composite material
Can find out by table 3, under the same same resin content of proportioning and same pressing process condition, dry method is suitable with wet method gained plate property, but the composite property of the dry legal preparation of wet mixing is much better than the matrix material of dry method or wet method gained; This be due to: by the first step wet method, there has been certain resin on glass surface, the resin compatible that this can get on next step dry process, thereby final optimization pass the consistency between glass and resin, thereby consistency and the cementability of glass and multipolymer are improved, optimize the system structure of matrix material, obtained better performance.
Further, we adopt the dry legal bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer-glass fiber composite material (referring to embodiment 14-17) of having prepared different proportionings of wet mixing, concrete preparation method is the same, wherein, glass quality accounts for 62.5 parts, and the quality of bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer accounts for 37.5 parts; Gained composite property is as shown in table 4:
The performance of table 4 bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer-glass fiber composite material
Embodiment 18-20 bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer-glass composite solid compound and preparation thereof
We obtain composite solid compound by the matrix material of embodiment 13 gained by thermal treatment, heat-treat condition is respectively: 340 DEG C/4h (embodiment 18), 360 DEG C/4h (embodiment 19), 380 DEG C/4h (embodiment 20), and the performance of gained cured article is as shown in table 5:
The performance of table 5 bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer-glass composite solid compound
As can be seen from Table 5, bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer-glass fiber composite material is through 340 DEG C/4h, the heat treated rear intensity of 360 DEG C/4h, modulus and thermotolerance are all improved significantly, although some reduces the heat treated material property performance of 380 DEG C/4h, but still is better than nonheat-treated matrix material.This is mainly because thermal treatment can improve the degree of bisphenol A-type bi-phthalonitrile/3-amino-benzene oxygen O-phthalic lonitrile copolymer-glass fiber composite material cross-linking density and curing reaction, thereby the mechanical property that makes material has lifting to a certain degree, but too high temperature and long time also can cause the decline of material property, this is mainly due to a small amount of small-molecule substance decomposition of material internal and multipolymer and glass surface action power change in high temperature.
Claims (14)
1. bi-phthalonitrile-3-amino-benzene oxygen O-phthalic lonitrile copolymer, is characterized in that, it is that bi-phthalonitrile and 3-amino-benzene oxygen phthalonitrile are obtained in 200～220 DEG C of melting copolymer-1 0-40min.
2. bi-phthalonitrile-3-amino-benzene oxygen O-phthalic lonitrile copolymer according to claim 1, is characterized in that, described bi-phthalonitrile is biphenyl type bi-phthalonitrile or bisphenol A-type bi-phthalonitrile.
3. the preparation method of the bi-phthalonitrile-3-amino-benzene oxygen O-phthalic lonitrile copolymer described in claim 1 or 2, it is characterized in that, the melting copolymer-1 0-40min at 200-220 DEG C by bi-phthalonitrile and 3-amino-benzene oxygen phthalonitrile, obtains bi-phthalonitrile-3-amino-benzene oxygen O-phthalic lonitrile copolymer.
4. the preparation method of bi-phthalonitrile-3-amino-benzene oxygen O-phthalic lonitrile copolymer according to claim 3, it is characterized in that, bi-phthalonitrile is stirred after melting at 200 DEG C-220 DEG C, continue to stir 5-10min, progressively add again 3-amino-benzene oxygen phthalonitrile to make its complete melting, then stir 10-30min.
5. bi-phthalonitrile-3-amino-benzene oxygen phthalonitrile cured article, is characterized in that, by the bi-phthalonitrile-3-amino-benzene oxygen O-phthalic lonitrile copolymer described in claim 1 or 2 pour into a mould, thermal treatment makes; Described heat-treat condition is to process 4-14h at 200-350 DEG C.
6. bi-phthalonitrile-3-amino-benzene oxygen phthalonitrile cured article according to claim 5, is characterized in that, described thermal treatment is for adopting Fractional Heat-treatment, heat-treat condition is: 200-220 DEG C/1-2h, 230-250 DEG C/1-4h, 260-290 DEG C/1-4h, 300-350 DEG C/1-4h.
7. bi-phthalonitrile-3-amino-benzene oxygen phthalonitrile cured article according to claim 6, is characterized in that, heat-treat condition is: 200 DEG C/2h, and 240 DEG C/2h, 280 DEG C/4h, 320 DEG C/4h.
8. according to the bi-phthalonitrile-3-amino-benzene oxygen phthalonitrile cured article described in claim 5-7 any one, it is characterized in that, gained cured article oxygen index is greater than 36%, flexural strength 88～130MPa, temperature of initial decomposition is greater than 478 DEG C, and 800 DEG C of carbon residue rates are greater than 65%.
9. a glass fibre reinforced composite material, it is characterized in that, it is taking glass and bi-phthalonitrile-3-amino-benzene oxygen O-phthalic lonitrile copolymer claimed in claim 1 as raw material, and the weight ratio of bi-phthalonitrile-3-amino-benzene oxygen O-phthalic lonitrile copolymer and glass is: 30～50 ︰ 70～50.
10. glass fibre reinforced composite material according to claim 9, is characterized in that, gained glass fibre reinforced composite material oxygen index is greater than 39%, flexural strength 525～710MPa, and temperature of initial decomposition is greater than 500 DEG C, and 800 DEG C of carbon residue rates are greater than 80%.
11. 1 kinds of glasses strengthen composite solid compounds, it is characterized in that, its be by the glass fibre reinforced composite material described in claim 9 or 10 pour into a mould, thermal treatment makes; Described heat-treat condition is to process 1-4h at 340-380 DEG C.
12. glasses according to claim 11 strengthen composite solid compound, it is characterized in that, heat-treat condition is: 340 DEG C/1-4h or 360 DEG C/1-4h or 380 DEG C/1-4h.
13. glasses according to claim 12 strengthen composite solid compound, it is characterized in that, heat-treat condition is: 340 DEG C/4h or 360 DEG C/4h or 380 DEG C/4h.
14. strengthen composite solid compound according to the glass described in claim 11-13 any one, it is characterized in that, gained glass strengthens composite solid compound flexural strength 701～723MPa, and temperature of initial decomposition is greater than 589 DEG C.
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