CN103193977A - Method for curing poly benzonitrile resin by amino phenoxy phthalonitrile - Google Patents
Method for curing poly benzonitrile resin by amino phenoxy phthalonitrile Download PDFInfo
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Abstract
The invention discloses a method for curing poly benzonitrile resin by amino phenoxy phthalonitrile. The method comprises the following steps of 1) adding aminophenol and anhydrous potassium carbonate to a reactor, adding a purified solvent, adding 4-nitrophthalonitrile after reacting for 1 hour at 80-100 DEG C, agitating and reacting for 4 hours and then cooling to room temperature, pouring into deionized water, filtering to obtain a reddish brown filter cake, and drying to obtain amino phenoxy phthalonitrile monomer for use; and 2) weighing bisphenol A-type phenoxy phthalonitrile monomer and the obtained amino phenoxy phthalonitrile, fully grinding, fusing, and vacuumizing to remove air bubbles, and transferring to a muffle furnace to cure, so as to obtain the poly benzonitrile resin. By adopting the obtained poly benzonitrile resin disclosed by the invention, the heat resistance and the mechanical property of the resin are improved; and the modulus of m-poly benzonitrile resin can be up to 4.3GPa at normal temperature, and is greatly improved by 1-3GPa in comparison with the resin obtained by aromatic amine in solidification, so that the application range of the resin is wider.
Description
Technical field
The invention belongs to the novel fire resistant macromolecule material preparation area, relate to a kind of method of utilizing the amino-benzene oxygen phthalonitrile to solidify metaphenylene and bisphenol A-type polyphenyl nitrile.
Background technology
Polyphenyl nitrile resin is to solidify the high temperature resistant thermosetting resin that forms by the phthalonitrile structural unit under the condition of catalyzer.Polyphenyl nitrile resin has excellent thermostability, thermo-oxidative stability, agent of low hygroscopicity, flame retardant resistance, chemical stability, mechanical property, has in fields such as machinery, aerospace, electronics, naval vessels widely to use.
Keller etc. are by changing the group that the monomer link connects, obtain the different polyphenyl nitrile resin of over-all properties, comprise: biphenyl type (Keller TM.Phthalonitrile-based high temperature resin.J Polym Sci, Part A:Polym Chem, 1988,26:3199-3212; Sastri SB, Keller TM.Phthalonitrile cure reaction with aromatic diamines.Journal of Polymer Science:Part A:Polymer Chemistry1998; 36:1885-1890.), metaphenylene (Keller TM, Dominguez DD.High temperature resorcinol-based phthalonitrile polymer.Polymer, 2005,46:4614-4618.), bisphenol A-type (Laskoski M, Dominguez DD, Keller TM.Synthesis and properties of a biphenyl A based phthalonitrile resin.J Polym.Sci., Part A:Polym.Chem., 2005,43:4136-4143.) and contain phenoxy group, cyanophenyl monomer [the U.S.P4 of sulfone chain link, 409,382 (1983)].Amir, Zhou (Zhou Heng) etc. have prepared and have contained amino autocatalysis o-phthalonitrile resin (Badshah Amir, Heng Zhou, Feng Liu, Hasan Aurangzeb.Synthesis and characterization of self-catalyzed imide-containing phthalonitrile resins.Journal of Polymer Science:Part A:Polymer Chemistry2010; 48:5916-5920.), (Heng Zhou, Amir Badashah, Zhenhua Luo, Feng Liu and Tong Zhao.Preparation and properties composition of ortho, meta and para autocatalytic phthaolonitrile compounds with amino group.Polymers advanced technologies2011; 22:1459-1465.), by the polyphenyl nitrile resin that self catalyzed reaction is polymerized, functional.People such as Liu Xiaobo utilize the phthalonitrile monomer (APN with autocatalysis function, 4-amino-benzene oxygen phthalonitrile) catalytic preparation contain biphenyl type polyphenyl nitrile (the Xiaoli Yang of aryl ether nitrile segments, Jindong Zhang, Yajie Lei, Jianchun Zhong, Xiaobo Liu.Effect of different amines on the crosslinking behavior and thermal properties of phthalonitrile oligomer containing biphenyl ethernitrile.Journal of applied polymer science2011; 121:2331-2337.).Liu Xiaobo etc. [amino-benzene oxygen phthalonitrile prepolymer, cured article and its production and use, CN102504252A] utilize amino-benzene oxygen phthalonitrile prepolymer that Resins, epoxy is solidified.
Above-mentioned cyanophenyl resin adopts aromatic amine to form as polymerization catalyst mostly, has shown resistance to elevated temperatures and mechanical property preferably, but still has amine small molecules volatilization phenomenon when being higher than 500 ℃, causes the inner gas hole defect that produces of resin.Appearance for fear of this problem, we will have the phthalonitrile monomer of autocatalysis function and introduce in the resin polymerization reaction process as solidifying agent, the catalysis metaphenylene, the bisphenol A-type phthalonitrile monomer, the resin that obtains is compared with the resin that uses traditional aromatic amine to solidify, has bigger process window, the resin that obtains with the phthalonitrile monomer self-polymerization with autocatalysis function (modulus :～1.7GPa) with APN catalysis contain aryl ether nitrile segments o-phthalonitrile resin (～3.2GPa) compare, have higher modulus (the metaphenylene polyphenyl nitrile resin modulus of 20%APPH catalysis :～4.3GPa), shown outstanding thermostability, more excellent through the resin property that after fixing obtains.
Technology contents
The present invention is directed to the small molecules volatilization at high temperature of traditional fragrant acid amides catalysis polyphenyl nitrile resin and cause the problem of resin defective, provide amino-benzene oxygen phthalonitrile monomer that a kind of utilization has the autocatalysis function as catalyzer, catalyzed and synthesized polyphenyl nitrile high molecular material; Compare as catalyzer with traditional aromatic amine, widened process window; Simultaneously, utilization has the amino-benzene oxygen phthalonitrile of autocatalysis function as catalyst to synthesize cyanophenyl resin, catalyst themselves is participated in the polyreaction, avoided the resin defective that the small molecules volatilization causes under the high temperature, obtain the more excellent polyphenyl nitrile resin of performance, can be used for high-tech sectors such as microelectronics, aerospace.
A kind of method of utilizing the amino-benzene oxygen phthalonitrile to solidify polyphenyl nitrile resin may further comprise the steps:
1) amino-benzene oxygen phthalonitrile (APPH) is synthetic: add amino-phenol and Anhydrous potassium carbonate in reactor, mol ratio is amino-phenol: Anhydrous potassium carbonate=1:1～1.2, proportioning according to 900-1000ml solvent/moles of phenol adds the solvent N of purifying then, dinethylformamide, 80～100 ℃ of reactions add the 4-nitrophthalonitrile after 1 hour, its proportioning is the mol ratio amino-phenol: 4-nitrophthalonitrile=1:1, stirring reaction was cooled to room temperature after 4 hours, pour into again in 7～8 times the deionized water of previous all adding volume of material sums, suction filtration then, obtain the reddish-brown filter cake, dry, obtain the amino-benzene oxygen phthalonitrile monomer, standby;
2) solidify: took by weighing the amino-benzene oxygen phthalonitrile that the cyanophenyl monomer that contains the bi-phthalonitrile group and last step obtain, its quality proportioning is for to contain bi-phthalonitrile cyanophenyl monomer: the mixed of amino-benzene oxygen phthalonitrile=95～80:5～20 is even, grind fully, it is transferred in the paper tinsel die cavity, place in the vacuum drying oven, fusion, vacuumize and remove bubble, treat the bubble Ex-all, be transferred in the retort furnace in 200～400 ℃ according to temperature programming, be cured reaction 14-22 hour, obtain polyphenyl nitrile resin.
Described amino-phenol is 4-amino-phenol, 3-amino-phenol or 2-amino-phenol;
Described amino-benzene oxygen phthalonitrile monomer 4-amino-benzene oxygen phthalonitrile, 3-amino-benzene oxygen phthalonitrile or 2-amino-benzene oxygen phthalonitrile;
Described solvent is N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone;
The described cyanophenyl monomer that contains the bi-phthalonitrile group, its general formula is:
N is natural number.
In the described cyanophenyl monomer that contains the bi-phthalonitrile group, when substituent R is
The time, n preferred 1～20.
The advantage that the present invention compares with background technology is: the amino-benzene oxygen phthalonitrile monomer that the present invention is prepared, only need 5 hours, and preparation time is short; Phthalonitrile monomer (amino-benzene oxygen phthalonitrile) the catalysis metaphenylene and the bisphenol A-type cyanophenyl monomer that have the autocatalysis function by use, make catalyzer participate in polyreaction, widened the process window of resin, avoided the defective of the resin that the small molecules volatilization causes under the high temperature, obtained the better polyphenyl nitrile resin of performance, improved the resin thermotolerance, mechanical property, under the modulus normal temperature of metaphenylene polyphenyl nitrile resin up to 4.3GPa, improve greatly than using aromatic amine to solidify the resin～3GPa that obtains, make the range of application of resin broader, can be used for microelectronics, high-tech sectors such as aerospace.
Description of drawings
Fig. 1. the DSC curve of amino-benzene oxygen phthalonitrile and bisphenol A-type cyanophenyl monomer reaction;
Fig. 2. the infared spectrum of amino-benzene oxygen phthalonitrile and bisphenol A-type cyanophenyl monomer reaction.
Embodiment
Synthesizing of 4-amino-benzene oxygen phthalonitrile monomer (APPH): in reactor, add 4-amino-phenol and Anhydrous potassium carbonate, mol ratio is 4-amino-phenol: Anhydrous potassium carbonate=1:1,4-amino-phenol 3.9362g(0.0361mol), Anhydrous potassium carbonate 5.0135g(0.0362mol) adds the solvent N of purifying according to the proportioning of 800ml/ moles of phenol then, dinethylformamide 30ml, react down about 80 ℃ and add 4-nitrophthalonitrile 6.2467g(0.0361mol after one hour), its mol ratio is than being the 4-amino-phenol: 4-nitrophthalonitrile=1:1, stir and react stopped reaction after 4 hours down, be cooled to room temperature, pour 7～8 times deionized water 300ml of previous all adding volume of material sums into, suction filtration, obtain the reddish-brown filter cake, dry 12 hours, obtain 4-amino-benzene oxygen phthalonitrile monomer, standby;
Solidify: it is even according to the mixed of 80:20 to take by weighing the cyanophenyl monomer and the 4-amino-benzene oxygen phthalonitrile monomer that contain the bi-phthalonitrile group, grind fully, it is transferred in the aluminium foil die cavity, place in the vacuum drying oven, fusion, vacuumize and remove bubble, treat the bubble Ex-all, be transferred in the retort furnace by 220 ℃/2 hours 250 ℃/4 hours, 280 ℃/6 hours, temperature programming (10 ℃/minute) in 320 ℃/6 hours is cured reaction, obtains polyphenyl nitrile resin.
The cyanophenyl monomer that contains the bi-phthalonitrile group described in the present embodiment, its structural formula is:
This kind method is solidified the resin obtain carry out the thermal weight loss experiment, it is as follows that the result is presented under air and the condition of nitrogen gas heat decomposition temperature:
(1) air: T
5%(metaphenylene cyanophenyl monomer: APPH=80:20)=522.10 ℃,
(2) nitrogen: T
5%(metaphenylene cyanophenyl monomer: APPH=80:20)=518.29 ℃, carbon yield (1000 ℃)=71.25%,
With 5%4, the resin T that 4 '-diaminodiphenyl oxide (ODA) solidifies
5%(air)=533 ℃, T
5%(nitrogen)=526 ℃, carbon yield (1000 ℃ of nitrogen)=72% is compared, and has shown outstanding high thermal resistance.
Dynamic mechanical (DMA) analysis shows, utilize the modulus of metaphenylene polyphenyl nitrile resin under 30 ℃ that 20% 4-amino-benzene oxygen phthalonitrile monomer (APPH) solidifies up to 4.265GPa, be higher than people such as Liu Xiaobo and utilize APN(4-amino-benzene oxygen phthalonitrile) solidify the polyphenyl nitrile resin that contains aryl ether nitrile segments～3.2GPa, be (～1.6GPa) about 2.5 times of the amino-benzene oxygen o-phthalonitrile resin modulus with autocatalysis function of all identical people's research.
Embodiment 2
Synthesizing of 4-amino-benzene oxygen phthalonitrile monomer (APPH): in reactor, add 4-amino-phenol and Anhydrous potassium carbonate, mol ratio is 4-amino-phenol: Anhydrous potassium carbonate=1:1,4-amino-phenol 3.9362g(0.0361mol), Anhydrous potassium carbonate 5.0135g(0.0362mol) adds the solvent dimethyl sulfoxide (DMSO) 30ml of purifying according to the proportioning of 800ml/ moles of phenol then, react down about 80 ℃ and add 4-nitrophthalonitrile 6.2467g(0.0361mol after one hour), its mol ratio is than being the 4-amino-phenol: 4-nitrophthalonitrile=1:1, stir and react stopped reaction after 4 hours down, be cooled to room temperature, pour among 7～8 times the deionized water 300ml of previous all adding volume of material sums, suction filtration, obtain the reddish-brown filter cake, dry 12 hours, obtain 4-amino-benzene oxygen phthalonitrile monomer, standby;
Solidify: the cyanophenyl monomer that contains the bi-phthalonitrile group according to mass ratio: the ratio of 4-amino-benzene oxygen phthalonitrile monomer=95:5, take by weighing bi-phthalonitrile cyanophenyl monomer and 4-amino-benzene oxygen phthalonitrile monomer, mixing the back grinds fully, it is transferred in the aluminium foil die cavity of rolling well in advance, place in the vacuum drying oven, fusion, vacuumize and remove bubble, treat the bubble Ex-all, be transferred in the retort furnace by 240 ℃/2 hours, 280 ℃/6 hours, 300 ℃/6 hours, temperature programming (10 ℃/minute), be cured reaction, obtain polyphenyl nitrile resin.
The cyanophenyl monomer that contains the bi-phthalonitrile group described in the present embodiment, its structural formula is:
Fig. 1 is the DSC(differential scanning calorimetric of 4-amino-benzene oxygen phthalonitrile monomer and bisphenol A-type monomer reaction) curve, as can be seen from the figure, use 4-amino-benzene oxygen phthalonitrile monomer can widen process window as catalyzer, the processing characteristics of resin is significantly improved.
Fig. 2 is the infrared spectrum of 4-amino-benzene oxygen phthalonitrile monomer and bisphenol A-type cyanophenyl monomer reaction, as can be seen from the figure, and along with the increase of the amount of 4-amino-benzene oxygen phthalonitrile monomer, 2230cm
-1The cyano group absorption peak at wave number place is more little, shows that the increase of hardener dose can make resin solidification more complete; At 1384cm
-1The absorption peak that goes out is classified as the absorption peak of triazine ring, illustrates in solidify reaction process, and the structure of resin is based on triazine ring.
This kind method is solidified the resin that obtains carry out the thermal weight loss experiment, the heat decomposition temperature that the result is presented under air and the condition of nitrogen gas is as follows:
(1) air: T
5%(bisphenol A-type cyanophenyl monomer: APPH=95:5)=471 ℃,
(2) nitrogen: T
5%(bisphenol A-type cyanophenyl monomer: APPH=95:5)=455 ℃, carbon yield (1000 ℃)=65%,
With 5%4, the resin T that 4 '-diaminodiphenyl oxide (ODA) solidifies
5%(air)=473 ℃, T
5%(nitrogen)=465 ℃, carbon yield (1000 ℃ of nitrogen)=67% is compared, and thermostability quite or superior has shown outstanding high thermal resistance.
Dynamic mechanical (DMA) shows that the polyphenyl nitrile resin that solidifies through 4-amino-benzene oxygen phthalonitrile monomer (APPH) has outstanding mechanical property, modulus～2.7GPa under the bisphenol A-type o-phthalonitrile resin normal temperature that 20%APPH solidifies.
Embodiment 3
Synthesizing of 3-amino-benzene oxygen phthalonitrile monomer: in reactor, add 3-amino-phenol and Anhydrous potassium carbonate, mol ratio is 3-amino-phenol: Anhydrous potassium carbonate=1:1,3-amino-phenol 3.3327g(0.0305mol), Anhydrous potassium carbonate 4.2203g(0.0305mol), proportioning according to the 800ml/ moles of phenol adds the solvent N of purifying then, dinethylformamide 25ml, react down about 80 ℃ and add 4-nitrophthalonitrile 5.2803g(0.0305mol after one hour), its mol ratio is than being the 3-amino-phenol: 4-nitrophthalonitrile=1:1, stir and react stopped reaction after 4 hours down, be cooled to room temperature, pour among 7～8 times the deionized water 250ml of previous all adding volume of material sums suction filtration into, obtain the reddish-brown filter cake, dry 12 hours, obtain 3-amino-benzene oxygen phthalonitrile monomer, standby;
Solidify: the cyanophenyl monomer that contains the bi-phthalonitrile group according to mass ratio: the ratio of 3-amino-benzene oxygen phthalonitrile monomer=90:10, take by weighing the cyanophenyl monomer and the 3-amino-benzene oxygen phthalonitrile monomer that contain the bi-phthalonitrile group, mix, grind fully, it is transferred in the aluminium foil die cavity, place in the vacuum drying oven, fusion, vacuumize and remove bubble, treat the bubble Ex-all, be transferred in the retort furnace by 240 ℃/2 hours 280 ℃/6 hours, 300 ℃/6 hours, temperature programming (10 ℃/minute) is cured reaction, obtains polyphenyl nitrile resin.
The cyanophenyl monomer that contains the bi-phthalonitrile group described in the present embodiment, its structural formula is:
Other steps are with among the embodiment 2, and the heat decomposition temperature of gained resin under air and condition of nitrogen gas is with example 2.
Embodiment 4
Synthesizing of 2-amino-benzene oxygen phthalonitrile monomer: in reactor, add 2-amino-phenol and Anhydrous potassium carbonate, mol ratio is 2-amino-phenol: Anhydrous potassium carbonate=1:1,2-amino-phenol 4.0522g(0.0371mol), Anhydrous potassium carbonate 5.2037g(0.0376mol), proportioning according to the 800ml/ moles of phenol adds the solvent N of purifying then, dinethylformamide 30ml, react down about 80 ℃ and add 4-nitrophthalonitrile 6.4229g(0.0371mol after one hour), its mol ratio is than being the 2-amino-phenol: 4-nitrophthalonitrile=1:1, stir and react stopped reaction after 4 hours down, be cooled to room temperature, pour among 7～8 times the deionized water 300ml of previous all adding volume of material sums suction filtration into, obtain the reddish-brown filter cake, dry 12 hours, obtain 2-amino-benzene oxygen phthalonitrile monomer, standby;
Solidify: it is even according to the mixed of 95:5 to take by weighing the cyanophenyl monomer and the 2-amino-benzene oxygen phthalonitrile monomer that contain the bi-phthalonitrile group, grind fully, it is transferred in the aluminium foil die cavity, place in the vacuum drying oven, fusion, vacuumize and remove bubble, treat the bubble Ex-all, be transferred in the retort furnace by 240 ℃/2 hours 280 ℃/6 hours, 300 ℃/6 hours, temperature programming (10 ℃/minute) is cured reaction, obtains polyphenyl nitrile resin.
The cyanophenyl monomer that contains the bi-phthalonitrile group described in the present embodiment, its structural formula is:
Other steps are with among the embodiment 2, and the heat decomposition temperature of gained resin under air and condition of nitrogen gas is with example 2.
Embodiment 5
Synthesizing of 4-amino-benzene oxygen phthalonitrile monomer (APPH): in reactor, add 4-amino-phenol and Anhydrous potassium carbonate, mol ratio is 4-amino-phenol: Anhydrous potassium carbonate=1:1,4-amino-phenol 3.5735g(0.0327mol), Anhydrous potassium carbonate 4.5360g(0.0328mol) adds the solvent N of purifying according to the proportioning of 800ml/ moles of phenol then, N-N,N-DIMETHYLACETAMIDE 30ml, react down about 80 ℃ and add 4-nitrophthalonitrile 5.6692g(0.0327mol after one hour), its mol ratio is than being the 4-amino-phenol: 4-nitrophthalonitrile=1:1, stir and react stopped reaction after 4 hours down, be cooled to room temperature, pour 7～8 times deionized water 300ml of previous all adding volume of material sums into, suction filtration, obtain the reddish-brown filter cake, dry 12 hours, obtain 4-amino-benzene oxygen phthalonitrile monomer, standby;
Solidify: it is even according to the mixed of 80:20 to take by weighing the cyanophenyl monomer and the 4-amino-benzene oxygen phthalonitrile monomer that contain the bi-phthalonitrile group, grinds fully, and it is transferred in the aluminium foil die cavity, place in the vacuum drying oven, fusion, vacuumize and remove bubble, treat the bubble Ex-all, be transferred in the retort furnace by 200 ℃/2 hours, 230 ℃/4 hours, 250 ℃/6 hours, 280 ℃/6 hours, temperature programming (10 ℃/minute) in 300 ℃/6 hours, be cured reaction, obtain polyphenyl nitrile resin.
The cyanophenyl monomer that contains the bi-phthalonitrile group described in the present embodiment, its structural formula is:
This kind method is solidified the resin obtain carry out the thermal weight loss experiment, it is as follows that the result is presented under air and the condition of nitrogen gas heat decomposition temperature:
(1) air: T
5%(butanols type cyanophenyl monomer: APPH=80:20)=512.19 ℃,
(2) nitrogen: T
5%(butanols type cyanophenyl monomer: APPH=80:20)=516.23 ℃, carbon yield (1000 ℃)=70.37%, the result shows that the resin of this kind structure has shown outstanding high thermal resistance.
Embodiment 6
Synthesizing of 4-amino-benzene oxygen phthalonitrile monomer (APPH): in reactor, add 4-amino-phenol and Anhydrous potassium carbonate, mol ratio is 4-amino-phenol: Anhydrous potassium carbonate=1:1,4-amino-phenol 3.7839g(0.0347mol), Anhydrous potassium carbonate 4.8013g(0.0347mol) adds the solvent N of purifying according to the proportioning of 800ml/ moles of phenol then, dinethylformamide 30ml, react down about 80 ℃ and add 4-nitrophthalonitrile 6.0097g(0.0347mol after one hour), its mol ratio is than being the 4-amino-phenol: 4-nitrophthalonitrile=1:1, stir and react stopped reaction after 4 hours down, be cooled to room temperature, pour 7～8 times deionized water 300ml of previous all adding volume of material sums into, suction filtration, obtain the reddish-brown filter cake, dry 12 hours, obtain 4-amino-benzene oxygen phthalonitrile monomer, standby;
Solidify: it is even according to the mixed of 90:10 to take by weighing the cyanophenyl monomer and the 4-amino-benzene oxygen phthalonitrile monomer that contain the bi-phthalonitrile group, grinds fully, and it is transferred in the aluminium foil die cavity, place in the vacuum drying oven, fusion, vacuumize and remove bubble, treat the bubble Ex-all, be transferred in the retort furnace by 200 ℃/2 hours, 230 ℃/4 hours, 250 ℃/6 hours, 280 ℃/6 hours, temperature programming (10 ℃/minute) in 300 ℃/6 hours, be cured reaction, obtain polyphenyl nitrile resin.
The cyanophenyl monomer that contains the bi-phthalonitrile group described in the present embodiment, its structural formula is:
This kind method is solidified the resin obtain carry out the thermal weight loss experiment, it is as follows that the result is presented under air and the condition of nitrogen gas heat decomposition temperature:
(1) air: T
5%(butanols type cyanophenyl monomer: APPH=80:20)=503.46 ℃,
(2) nitrogen: T
5%(butanols type cyanophenyl monomer: APPH=80:20)=507.55 ℃, carbon yield (1000 ℃)=69.49%, the result shows that the resin of this kind structure has shown outstanding high thermal resistance.
Embodiment 7
Synthesizing of 4-amino-benzene oxygen phthalonitrile monomer (APPH): in reactor, add 4-amino-phenol and Anhydrous potassium carbonate, mol ratio is 4-amino-phenol: Anhydrous potassium carbonate=1:1,4-amino-phenol 4.0026g(0.0367mol), Anhydrous potassium carbonate 5.1024g(0.0368mol) adds the solvent N-Methyl pyrrolidone 30ml of purifying according to the proportioning of 800ml/ moles of phenol then, react down about 80 ℃ and add 4-nitrophthalonitrile 6.3501g(0.0367mol after one hour), its mol ratio is than being the 4-amino-phenol: 4-nitrophthalonitrile=1:1, stir and react stopped reaction after 4 hours down, be cooled to room temperature, pour 7～8 times deionized water 300ml of previous all adding volume of material sums into, suction filtration, obtain the reddish-brown filter cake, dry 12 hours, obtain 4-amino-benzene oxygen phthalonitrile monomer, standby;
Solidify: it is even according to the mixed of 80:20 to take by weighing the cyanophenyl monomer and the 4-amino-benzene oxygen phthalonitrile monomer that contain the bi-phthalonitrile group, grinds fully, and it is transferred in the aluminium foil die cavity, place in the vacuum drying oven, fusion, vacuumize and remove bubble, treat the bubble Ex-all, be transferred in the retort furnace by 240 ℃/2 hours, 270 ℃/4 hours, 290 ℃/6 hours, 315 ℃/6 hours, temperature programming (10 ℃/minute) in 340 ℃/6 hours, be cured reaction, obtain polyphenyl nitrile resin.
The cyanophenyl monomer that contains the bi-phthalonitrile group described in the present embodiment, its structural formula is:
This kind method is solidified the resin obtain carry out the thermal weight loss experiment, it is as follows that the result is presented under air and the condition of nitrogen gas heat decomposition temperature:
(1) air: T
5%(biphenyl type cyanophenyl monomer: APPH=80:20)=535.68 ℃,
(2) nitrogen: T
5%(biphenyl type cyanophenyl monomer: APPH=80:20)=538.69 ℃, carbon yield (1000 ℃)=72.56%,
The result shows that the resin of this kind structure has shown outstanding high thermal resistance.
Described chemical reagent is commercially available acquisition.
Unaccomplished matter of the present invention is known technology.
Claims (6)
1. method of utilizing the amino-benzene oxygen phthalonitrile to solidify polyphenyl nitrile resin is characterized by and may further comprise the steps:
1) amino-benzene oxygen phthalonitrile monomer (APPH) is synthetic: add amino-phenol and Anhydrous potassium carbonate in reactor, mol ratio is amino-phenol: Anhydrous potassium carbonate=1:1～1.2, proportioning according to 900-1000ml solvent/moles of phenol adds the solvent of purifying then, 80～100 ℃ of reactions add the 4-nitrophthalonitrile after 1 hour, its proportioning is the mol ratio amino-phenol: 4-nitrophthalonitrile=1:1, stirring reaction was cooled to room temperature after 4 hours, pour into again in 7～8 times the deionized water of previous all adding volume of material sums, suction filtration then, obtain the reddish-brown filter cake, drying obtains the amino-benzene oxygen phthalonitrile monomer, and is standby;
2) solidify: took by weighing the amino-benzene oxygen phthalonitrile that the cyanophenyl monomer that contains the bi-phthalonitrile group and last step obtain, its quality proportioning is the cyanophenyl monomer that contains the bi-phthalonitrile group: the mixed of amino-benzene oxygen phthalonitrile=95～80:5～20 is even, grind fully, it is transferred in the paper tinsel die cavity, place in the vacuum drying oven, fusion, vacuumize and remove bubble, treat the bubble Ex-all, be transferred in the retort furnace in 200～400 ℃ according to temperature programming, be cured reaction 15-22 hour, obtain polyphenyl nitrile resin.
2. the method for utilizing the amino-benzene oxygen phthalonitrile to solidify polyphenyl nitrile resin as claimed in claim 1, it is characterized by described amino-phenol is 4-amino-phenol, 3 amino-phenols or 2 amino-phenols.
3. described amino-benzene oxygen phthalonitrile monomer 4-amino-benzene oxygen phthalonitrile, 3-amino-benzene oxygen phthalonitrile or 2-amino-benzene oxygen phthalonitrile.
4. the method for utilizing the amino-benzene oxygen phthalonitrile to solidify polyphenyl nitrile resin as claimed in claim 1, it is characterized by described solvent is N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone.
5. the method for utilizing the amino-benzene oxygen phthalonitrile to solidify polyphenyl nitrile resin as claimed in claim 1, it is characterized by the described cyanophenyl monomer that contains the bi-phthalonitrile group, its general formula is: the described cyanophenyl monomer that contains the bi-phthalonitrile group, and its general formula is:
6. the method for utilizing the amino-benzene oxygen phthalonitrile to solidify polyphenyl nitrile resin as claimed in claim 5 is characterized by in the described cyanophenyl monomer that contains the bi-phthalonitrile group, when substituent R is
The time, n=1～20.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN108117644A (en) * | 2018-01-16 | 2018-06-05 | 河北工业大学 | A kind of method for preparing naphthalene self-catalysis type polyphenyl nitrile resin |
| CN108442122A (en) * | 2018-04-26 | 2018-08-24 | 湖南师范大学 | Sizing agent for preparing quartz fiber/nitrile resin composite material |
| CN108642889A (en) * | 2018-04-26 | 2018-10-12 | 湖南师范大学 | High-temperature-resistant carbon fiber sizing agent |
| CN109096488A (en) * | 2017-06-21 | 2018-12-28 | 中国人民解放军国防科学技术大学 | O-phthalonitrile resin composition and preparation method thereof |
| CN109694476A (en) * | 2019-01-07 | 2019-04-30 | 河北工业大学 | A method of preparing the type poly-o-phthalonitrile resin of self-catalysis containing urea groups |
| CN111393642A (en) * | 2020-05-26 | 2020-07-10 | 河北工业大学 | Preparation method of fluorine-containing autocatalytic phthalonitrile resin |
| CN112961323A (en) * | 2021-03-25 | 2021-06-15 | 广东炜林纳新材料科技股份有限公司 | Fluorinated benzonitrile and fluorinated epoxy resin composite material and preparation method thereof |
| CN113913013A (en) * | 2021-11-18 | 2022-01-11 | 航天特种材料及工艺技术研究所 | Structural bearing-ablation integrated phthalonitrile resin and preparation method and application thereof |
| CN114085524A (en) * | 2021-11-18 | 2022-02-25 | 航天特种材料及工艺技术研究所 | Structural bearing-ablation integrated phthalonitrile resin prepreg, composite material and preparation method thereof |
| CN115504907A (en) * | 2022-09-15 | 2022-12-23 | 河北工业大学 | Phthalonitrile monomer containing binaphthyl structure and resin thereof |
| CN115650879A (en) * | 2022-09-27 | 2023-01-31 | 电子科技大学 | Amino phenoxy phthalonitrile resin, polymer and preparation method thereof |
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| CN106939080B (en) * | 2016-01-04 | 2020-01-03 | 中国人民解放军国防科学技术大学 | Nitrile-based resin mixture and preparation method thereof |
| CN106939080A (en) * | 2016-01-04 | 2017-07-11 | 中国人民解放军国防科学技术大学 | Cyano resin mixture and preparation method thereof |
| CN109096488B (en) * | 2017-06-21 | 2021-02-26 | 中国人民解放军国防科学技术大学 | Phthalonitrile resin composition and preparation method thereof |
| CN109096488A (en) * | 2017-06-21 | 2018-12-28 | 中国人民解放军国防科学技术大学 | O-phthalonitrile resin composition and preparation method thereof |
| CN108117644A (en) * | 2018-01-16 | 2018-06-05 | 河北工业大学 | A kind of method for preparing naphthalene self-catalysis type polyphenyl nitrile resin |
| CN108442122A (en) * | 2018-04-26 | 2018-08-24 | 湖南师范大学 | Sizing agent for preparing quartz fiber/nitrile resin composite material |
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| CN109694476A (en) * | 2019-01-07 | 2019-04-30 | 河北工业大学 | A method of preparing the type poly-o-phthalonitrile resin of self-catalysis containing urea groups |
| CN111393642B (en) * | 2020-05-26 | 2022-07-26 | 河北工业大学 | Preparation method of fluorine-containing autocatalytic phthalonitrile resin |
| CN111393642A (en) * | 2020-05-26 | 2020-07-10 | 河北工业大学 | Preparation method of fluorine-containing autocatalytic phthalonitrile resin |
| CN112961323A (en) * | 2021-03-25 | 2021-06-15 | 广东炜林纳新材料科技股份有限公司 | Fluorinated benzonitrile and fluorinated epoxy resin composite material and preparation method thereof |
| CN113913013A (en) * | 2021-11-18 | 2022-01-11 | 航天特种材料及工艺技术研究所 | Structural bearing-ablation integrated phthalonitrile resin and preparation method and application thereof |
| CN114085524A (en) * | 2021-11-18 | 2022-02-25 | 航天特种材料及工艺技术研究所 | Structural bearing-ablation integrated phthalonitrile resin prepreg, composite material and preparation method thereof |
| CN113913013B (en) * | 2021-11-18 | 2023-09-29 | 航天特种材料及工艺技术研究所 | Structural bearing-ablation integrated phthalonitrile resin and preparation method and application thereof |
| CN114085524B (en) * | 2021-11-18 | 2023-09-29 | 航天特种材料及工艺技术研究所 | Structural bearing-ablation integrated phthalonitrile resin prepreg, composite material and preparation method thereof |
| CN115504907A (en) * | 2022-09-15 | 2022-12-23 | 河北工业大学 | Phthalonitrile monomer containing binaphthyl structure and resin thereof |
| CN115504907B (en) * | 2022-09-15 | 2023-11-17 | 河北工业大学 | Phthalonitrile monomer containing binaphthyl structure and resin thereof |
| CN115650879A (en) * | 2022-09-27 | 2023-01-31 | 电子科技大学 | Amino phenoxy phthalonitrile resin, polymer and preparation method thereof |
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