CN101914038A - Bisphenol A type bis-phthalonitrile resin with aryl ether nitrile segments, cured product and preparation method thereof - Google Patents
Bisphenol A type bis-phthalonitrile resin with aryl ether nitrile segments, cured product and preparation method thereof Download PDFInfo
- Publication number
- CN101914038A CN101914038A CN2010102272271A CN201010227227A CN101914038A CN 101914038 A CN101914038 A CN 101914038A CN 2010102272271 A CN2010102272271 A CN 2010102272271A CN 201010227227 A CN201010227227 A CN 201010227227A CN 101914038 A CN101914038 A CN 101914038A
- Authority
- CN
- China
- Prior art keywords
- bisphenol
- aryl ether
- ether nitrile
- type
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a bisphenol A type bis-phthalonitrile resin with aryl ether nitrile segments, a cured product and a preparation method thereof and belongs to the field of polymer materials. Raw materials of bisphenol A and 2,6-dichlorobenzonitrile are subjected to nucleophilic substitution reaction, anhydrous potassium carbonate and anhydrous sodium carbonate are used as a catalyst, a hydroxyl-terminated bisphenol A type oligomer intermediate is formed in mixed liquor of a strong polar solvent and toluene, and then hydroxyl groups are substituted by 4-nitrophthalonitrile, thus obtaining the resin. A cure-crosslinking agent, the mass of which is equal to 5 percent of the resin, is added into the resin, and then after pre-curing at 220-240DEG C and heat treatment at 375DEG C at least, the cured product of the resin can be obtained. The bis-phthalonitrile resin provided by the invention has different chain lengths and the aryl ether nitrile segments as well as a low melting point and wider curing process temperature, and the cured product is of a net structure which comprises a phthalocyanine ring and a triazine ring and has excellent heat stability. The manufacturing methods of the resin and the cured product are simple and controllable and are suitable for industrial production.
Description
Technical field
The invention belongs to polymeric material field, relate to the bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments, cured article and preparation method thereof.
Background technology
O-phthalonitrile resin as resistant to elevated temperatures type material the eighties in 20th century Keller and the team thereof by US Naval Research Laboratory develop the earliest.Because completely crued O-phthalic nitrile polymer has good thermostability and mechanical property, and good thermo-oxidative stability, flame retardant resistance and higher moisture resistivity, thereby this resinoid has purposes widely in fields such as aerospace, naval vessel, microelectronics and machinofacture.
Bi-phthalonitrile (BPh) is the most sophisticated high-performance thermosetting resin matrix (monomer) that is studied at present, and it can form the polymkeric substance (cured article) of high crosslink density under the effect of linking agent.This cured article has excellent mechanical property and thermostability: in temperature mechanical property stable for extended periods of time during up to 371 ℃; When temperature reaches 450 ℃, glass transition still do not occur or take place softening.Simultaneously, chemical stability, flame retardant resistance, moistureproofness and the processibility of bi-phthalonitrile resin polymkeric substance (cured article) are better than resins such as traditional Resins, epoxy, bismaleimides far away also than more excellent.Yet; the melt temperature of bi-phthalonitrile resin (monomer) is up to 235 ℃; only than low 20 ℃ of its curing reaction temperature; this makes that its processing temperature window is too narrow; and its thermofixation reaction is very slow; if just thermofixation need be handled at 280 ℃ and just can observe tangible gel in nearly hundred hours.So narrow process window and slowly solidification rate had a strong impact on the processibility and the overall application of this kind resin.
In recent years, in order to improve the processing characteristics of bi-phthalonitrile resin, Keller has successively synthesized at the low-melting bi-phthalonitrile of three classes.At High.Perform.Polym., 2006, report has synthesized Resorcinol class bi-phthalonitrile oligopolymer in 18:283-304 one literary composition; At J.Polym.Sci., Part A:Polym.Chem, 2005, the report report has synthesized and has contained the unitary bi-phthalonitrile of aromatic ether ketone in 43:4136-4143 one literary composition; At Polymer, 2007, report has synthesized and has contained the unitary bi-phthalonitrile of aromatic oxide-phosphorus oxide in 48:6234-6240 one literary composition.Though the monomeric exploitation of these low melting points has solved the too narrow problem of processing temperature window, these low melting point monomers often need higher after fixing temperature.Aromatic ether ketone banded O-phthalic eyeball monomer that Keller was delivered in 2005 and the monomeric after fixing temperature of being delivered in 2006 of polyethers banded O-phthalic eyeball even up to 425 ℃.And the temperature of being delivered in 2007 of fusing fully that contains the unitary bi-phthalonitrile of aromatic oxide-phosphorus oxide has reached 150 ℃.Though the processing temperature window has been widened in the reduction of fusing point, the too high problem of after fixing temperature never is well solved.
At present, do not see the preparation method's of bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments that low melting point, after fixing temperature are relatively low and cured article thereof report as yet.
Summary of the invention
The invention provides a kind of bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments, cured article and preparation method thereof.The bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments that is provided is a kind of oligopolymer, because of the aryl ether nitrile segments with lower fusing point and different lengths makes the more existing bi-phthalonitrile of this resin have wideer processing temperature window.The bisphenol A-type bi-phthalonitrile resin cured article that contains aryl ether nitrile segments that is provided has and is easy to solidify machine-shaping, does not sacrifice its excellent mechanical property, thermostability and other performances simultaneously.Preparation method's simple controllable of resin that is provided and cured article thereof is suitable for suitability for industrialized production.
Technical solution of the present invention is:
(1) contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments.
A kind of bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments, shown in figure l, its structural formula is:
N=2 wherein, 4,6 or 8.
(2) contain the preparation method of the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments.
A kind of preparation method who contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments as shown in Figure 2, may further comprise the steps:
Step l: with dihydroxyphenyl propane, 2,6-dichlorobenzene eyeball, catalyzer, solvent add and have in the reaction vessel of division box, are heated to 130～160 ℃ of following back flow reaction 3～6 hours; Emit reaction generates in the water trap water byproduct and toluene then, continuing to heat up distills out toluene postcooling residual in the reaction system to room temperature.
Step 2: in the described reaction vessel that has a division box of step 1, add 4-nitro bi-phthalonitrile, 80～100 ℃ of reactions 5～10 hours down.
Step 3: with precipitation in the HCl solution of the reaction mixture impouring 0.1mol/L of step 2, filter, with a large amount of distilled water washs to neutral, thorough drying, acquisition contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments.
Wherein, dihydroxyphenyl propane, 2, the mole proportioning of 6-dichlorobenzonitrile, catalyzer, solvent, 4-nitrophthalonitrile is:
Described catalyzer is Anhydrous potassium carbonate or anhydrous sodium carbonate, and described solvent is 5: 1 the intensive polar solvent and the mixed solution of toluene for the mole proportioning, and wherein intensive polar solvent is N-Methyl pyrrolidone or N, dinethylformamide.
(3) contain the cured article of the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments
A kind of cured article that contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments is the polymkeric substance that contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments, and its structure is the reticulated structure (as shown in Figure 3) that comprises π-pi-conjugated phthalocyanine ring and triazine ring.Wherein, the described structural formula that contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments is:
N=2 wherein, 4,6 or 8;
The structural formula of described phthalocyanine ring is (seeing Fig. 3 (a)):
The structural formula of described triazine ring is (seeing Fig. 3 (b)):
(4) contain the preparation method of the bisphenol A-type bi-phthalonitrile resin cured article of aryl ether nitrile segments.
A kind of preparation method who contains the bisphenol A-type bi-phthalonitrile resin cured article of aryl ether nitrile segments as shown in Figure 4, may further comprise the steps:
Step 1: the bisphenol A-type bi-phthalonitrile resin that will contain aryl ether nitrile segments mixes with the cure-crosslinking agent that is equivalent to its 5% quality, and 220～240 ℃ of following Procuring reactions 10～20 minutes, obtains prepolymer;
Step 2: the prepolymer of step 1 gained had been not less than under 375 ℃ the temperature condition thermal treatment 8～12 hours, the cured article of the bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments of acquisition.
Wherein:
The described structural formula that contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments is:
N=2 wherein, 4,6 or 8.
Described cure-crosslinking agent is: 2,6-two-4-amino-benzene oxygen cyanobenzene (BDB), 4,4 '-diaminodiphenylsulfone(DDS) (DDS), 1,3-two-3-amino-benzene oxygen benzene (m-APB), 1, any one in 4-two-4-amino-benzene oxygen benzene (p-APB), 3-amino-benzene oxygen-4-phenyl two sulfones (m-BAPS) or 4-amino-benzene oxygen-4-phenyl two sulfones (p-BAPS).
Reaction mechanism of the present invention can be described below:
The bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments provided by the present invention is by dihydroxyphenyl propane and 2, the nucleophilic substitution reaction of 6-dichlorobenzonitrile, with Anhydrous potassium carbonate or anhydrous sodium carbonate is catalyzer, in the mole proportioning is to form a kind of hydroxy-end capped bisphenol A-type oligopolymer intermediate in intensive polar solvent/toluene mixture liquid of 5: 1, hydroxyl in the intermediate replaces with the 4-nitrophthalonitrile then, thereby has formed the described bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments.
The bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments provided by the present invention why can under the catalysis of cure-crosslinking agent, be cured be because bi-phthalonitrile resin in cyano group can under certain heating condition polyaddition reaction take place.People such as Keller find: in amine catalysis bi-phthalonitrile polymeric process, aromatic diamine can provide necessary two moles of electronics in the process that forms the phthalocyanine ring.In addition, people such as Burchill think that amine or organic acid amine salt do the catalytic cyano group crosslinking reaction of linking agent, and its product is based on the triazine ring compound.What form is the network structure of cross-linking set with fragrant heterocycles such as phthalocyanine ring and triazine rings, has given the thermotolerance of this kind resin excellence.
The present invention contains the bi-phthalonitrile resin of aryl ether nitrile segments and the structure of cured article uses Fourier infrared (FTIR) spectrograph to carry out characterization test.The bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments among the present invention and the thermal analysis experiment of cured article thereof adopt the differential scanning calorimeter MQ100 (DSC) and the thermal gravimetric analyzer Q50 of U.S. TA company of U.S. TA company to carry out.Wherein, the fusing point of resin and curing summit temperature adopt DSC10 ℃/min to test; Carbon yield when decomposing 5% o'clock temperature and 800 ℃ adopts TGA20 ℃/min to test.
The bi-phthalonitrile resin that contains aryl ether nitrile segments and the cured article thereof of the present invention's preparation use Fourier infrared (FTIR) spectrograph to carry out characterization test to its structure.Wherein, the charateristic avsorption band of the prepared bi-phthalonitrile resin that contains aryl ether nitrile segments exists: 2967cm
-1(-CH3); 2230cm
-1(CN); 1246,1208cm
-1(Ar-O-Ar); 832,782,729cm
-1(phenyl ring), this test result show the bi-phthalonitrile resin (because of having occurred above charateristic avsorption band on the resin infared spectrum) that has obtained containing aryl ether nitrile segments.The charateristic avsorption band of the cured article of the prepared bi-phthalonitrile resin that contains aryl ether nitrile segments exists: 1010cm
-1(phthalocyanine ring); 1360cm
-1And 1520cm
-1(triazine ring); 1246,1208cm
-1(ehter bond); 832,782,729cm
-1(phenyl ring), this test result show the bi-phthalonitrile resin cured article (having occurred above charateristic avsorption band on the infared spectrum because of resin cured matter) that has obtained containing aryl ether nitrile segments.
The performance perameter that contains the bi-phthalonitrile resin of aryl ether nitrile segments provided by the invention is:
Fusing point: 50-70 ℃;
DSC solidifies peak temperature 220-240 ℃;
The temperature of decomposition 5%: 500-560 ℃;
800 ℃ carbon yield: 66-78%.
The bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments provided by the invention is a kind of the having excellent shaping performance and have the macromolecule resin matrix of extensive use of the flexible aryl ether nitrile segments of introducing of new acquisition.It is that main raw material curing makes that the bisphenol A-type bi-phthalonitrile resin cured article that contains aryl ether nitrile segments provided by the invention is to use the bi-phthalonitrile resin that contains aryl ether nitrile segments, has activity of curing reaction preferably, water-intake rate is extremely low, has the resistance to elevated temperatures of bi-phthalonitrile.The adding of cure-crosslinking agent amine had both reduced the curing processing temperature significantly, had widened the process window of system, can use under harsher hot environment again.In addition, resin cured matter of the present invention contains polarity CN group, can increase cementability and affinity with material greatly, to be used to prepare high performance composite; Have reactable with metal ion, be applied to the better effects if of metal high temperature resistant adhesive; Have insulativity, can be used for the high-temperature insulation material field.Preparation method of the present invention is simply effective, the reaction process simple controllable, and product has good market outlook.
In sum, technical characterstic of the present invention be following some:
1, by regulating ratio raw materials used and prescription, can obtain the bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments of a series of different chain length.
2, between the end group of phthalonitrile, introduce flexible aryl ether nitrile segments, effectively reduced the fusing point of bi-phthalonitrile resin, widened the process window of system.
3, use the aromatic diamine of different structure to be cure-crosslinking agent, can in very large range regulate and control the structure and the performance of cured product by regulating the kind and the proportioning of amine.
4, cured article is mainly π-pi-conjugated phthalocyanine ring structure and the triazine ring structure with specific function, thereby gives material very high thermal stability.
Description of drawings
Fig. 1 is the structural formula that contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments provided by the invention.
Fig. 2 is the preparation method's schematic flow sheet that contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments provided by the invention.
Fig. 3 is the structural formula of phthalocyanine ring and triazine ring in the bisphenol A-type bi-phthalonitrile resin cured article that contains aryl ether nitrile segments provided by the invention.
Fig. 4 is the bisphenol A-type bi-phthalonitrile resin cured article preparation method schematic flow sheet that contains aryl ether nitrile segments provided by the invention.
Embodiment
Below the present invention will be further described for the description by embodiment, but this is not a limitation of the present invention, and those skilled in the art can make various modification or modification according to basic thought of the present invention, only otherwise break away from basic thought of the present invention, all within the scope of the present invention.
Embodiment one
The present invention contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments (n=2) and the preparation of cured article thereof
(1) contain bisphenol A-type bi-phthalonitrile resin synthetic of aryl ether nitrile segments (n=2):
Step 1: with dihydroxyphenyl propane, 2,6-dichlorobenzonitrile, Anhydrous potassium carbonate, N, dinethylformamide/toluene mixed solvent is added in the reaction vessel that has division box, is heated to 130 ℃ of back flow reaction 6 hours; Emit reaction generates in the water trap water byproduct and toluene then, continuing to heat up distills out toluene postcooling residual in the reaction system to room temperature.
Step 2: in the described reaction vessel that has a division box of step 1, add 4-nitro bi-phthalonitrile, 90 ℃ of reactions 6 hours down.
Step 3: precipitate in the HCl solution with the reaction mixture impouring 0.1mol/L of step 2, filter, with a large amount of distilled water washs to neutral, 90 ℃ dry 12 hours down, acquisition contains (n=2) bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments.
Wherein, dihydroxyphenyl propane, 2,6-dichlorobenzonitrile, Anhydrous potassium carbonate, N, the mole proportioning of dinethylformamide/toluene mixed solvent, 4-nitrophthalonitrile is:
The bisphenol A-type bi-phthalonitrile resin fusing point that contains aryl ether nitrile segments (n=2) that makes thus is 58 ℃, and solidifying summit temperature is 223 ℃.The infared spectrum of this resin is at 2967cm
-1(CH
3); 2231cm
-1(CN); 1246,1208cm
-1(Ar-O-Ar); 832,782,729cm
-1(phenyl ring) locates to have occurred charateristic avsorption band, shows the bisphenol A-type bi-phthalonitrile resin that has obtained containing aryl ether nitrile segments (n=2).
(2) contain the preparation of the bisphenol A-type bi-phthalonitrile resin cured article of aryl ether nitrile segments (n=2):
Step 1: the bisphenol A-type bi-phthalonitrile resin and the cure-crosslinking agent-2 that is equivalent to its 5% quality that will contain aryl ether nitrile segments (n=2), 6-two-4-amino-benzene oxygen cyanobenzene (BDB) mixes, and carries out Procuring at 220～240 ℃ and obtains prepolymer in 15 minutes;
Step 2: the prepolymer of step 1 gained was heat-treated the cured article of the bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments (n=2) of acquisition 8 hours being not less than under 375 ℃ the temperature condition.
This resin cured matter is at 1010cm
-1(phthalocyanine ring); 1360cm
-1And 1520cm
-1(triazine ring); 1246,1208cm
-1(Ar-O-Ar); 832,782,729cm
-1(phenyl ring) locates all to have occurred charateristic avsorption band, shows the bisphenol A-type bi-phthalonitrile resin cured article that has obtained containing aryl ether nitrile segments (n=2).According to the resin cured matter of this step preparation 375 ℃ handle 8 hours after, the temperature of decomposing 5% o'clock is 510 ℃; Carbon yield under 800 ℃ the nitrogen atmosphere is 75%.
Embodiment two
The present invention contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments (n=4) and the preparation of cured article thereof.
(1) contain bisphenol A-type bi-phthalonitrile resin synthetic of aryl ether nitrile segments (n=4):
Step 1: with dihydroxyphenyl propane, 2,6-dichlorobenzonitrile, Anhydrous potassium carbonate, N, dinethylformamide/toluene mixed solvent is added in the reaction vessel that has division box, is heated to 150 ℃ of following back flow reaction 3.5 hours; Emit reaction generates in the water trap water byproduct and toluene then, continuing to heat up distills out toluene postcooling residual in the reaction system to room temperature.
Step 2: in the described reaction vessel that has a division box of step 1, add 4-nitro bi-phthalonitrile, 85 ℃ of reactions 9.5 hours down.
Step 3: precipitate in the HCl solution with the reaction mixture impouring 0.1mol/L of step 2, filter, with a large amount of distilled water washs to neutral, 90 ℃ dry 12 hours down, acquisition contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments (n=4).
Wherein, dihydroxyphenyl propane, 2,6-dichlorobenzonitrile, Anhydrous potassium carbonate, N, the mole proportioning of dinethylformamide/toluene mixed solvent, 4-nitrophthalonitrile is:
The bisphenol A-type bi-phthalonitrile resin fusing point that contains aryl ether nitrile segments (n=4) that makes thus is 62 ℃, and solidifying summit temperature is 227 ℃.The infared spectrum of this resin is at 2967cm
-1(CH
3); 2231cm
-1(CN); 1246,1208cm
-1(Ar-O-Ar); 832,782,729cm
-1(phenyl ring) locates to have occurred charateristic avsorption band, shows the bisphenol A-type bi-phthalonitrile resin that has obtained containing aryl ether nitrile segments (n=4)
(2) contain the preparation of the bisphenol A-type bi-phthalonitrile resin cured article of aryl ether nitrile segments (n=4):
Step 1: will contain the bisphenol A-type bi-phthalonitrile resin and the cure-crosslinking agent-2 that is equivalent to its 5% quality of aryl ether nitrile segments (n=2), 6-two-4-amino-benzene oxygen cyanobenzene (BDB) mixes, and obtains prepolymer in 15 minutes 230 ℃ of following Procuring.;
Step 2: the prepolymer of step 1 gained was heat-treated the cured article of (n=4) bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments of acquisition 8 hours being not less than under 375 ℃ the temperature condition.
This resin cured matter is at 1010cm
-1(phthalocyanine ring); 1360cm
-1And 1520cm
-1(triazine ring); 1246,1208cm
-1(Ar-O-Ar); 832,782,729cm
-1(phenyl ring) locates all to have occurred charateristic avsorption band, shows (n=4) bisphenol A-type bi-phthalonitrile resin cured article that has obtained containing aryl ether nitrile segments.According to the resin cured matter of this step preparation 375 ℃ handle 8h after, the temperature of decomposing 5% o'clock is 509 ℃; Carbon yield under 800 ℃ the nitrogen atmosphere is 74%.
Embodiment three
The present invention contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments (n=6) and the preparation of cured article thereof.
(1) contain bisphenol A-type bi-phthalonitrile resin synthetic of aryl ether nitrile segments (n=6):
Step 1: with dihydroxyphenyl propane, 2,6-dichlorobenzonitrile, Anhydrous potassium carbonate, N-Methyl pyrrolidone/toluene mixed solvent are added in the reaction vessel that has division box, are heated to 160 ℃ of back flow reaction 3 hours; Emit reaction generates in the water trap water byproduct and toluene then, continuing to heat up distills out toluene postcooling residual in the reaction system to room temperature.
Step 2: in the described reaction vessel that has a division box of step 1, go into 4-nitro bi-phthalonitrile, 90 ℃ of reactions 9 hours.
Step 3: precipitate in the HCl solution with the reaction mixture impouring 0.1mol/L of step 2, filter, with a large amount of distilled water washs to neutral, oven dry is dry 12 hours in 90 ℃ of baking ovens, acquisition contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments (n=6).
Wherein, dihydroxyphenyl propane, 2,6-dichlorobenzonitrile, Anhydrous potassium carbonate, N, the mole proportioning of dinethylformamide/toluene mixed solvent, 4-nitrophthalonitrile is:
The bisphenol A-type bi-phthalonitrile resin fusing point that contains aryl ether nitrile segments (n=6) that makes thus is 66 ℃, and solidifying summit temperature is 229 ℃.The infared spectrum of this resin is at 2967cm
-1(CH
3); 2231cm
-1(CN); 1246,1208cm
-1(Ar-O-Ar); 832,782,729cm
-1(phenyl ring) locates to have occurred charateristic avsorption band, shows the bisphenol A-type bi-phthalonitrile resin that has obtained containing aryl ether nitrile segments (n=6)
(2) contain the preparation of the bisphenol A-type bi-phthalonitrile resin cured article of aryl ether nitrile segments (n=6):
Step 1: the bisphenol A-type bi-phthalonitrile resin and the cure-crosslinking agent-2 that is equivalent to its 5% quality that will contain aryl ether nitrile segments (n=6), 6-two-4-amino-benzene oxygen cyanobenzene (BDB) mixes, and carries out Procuring at 220～240 ℃ and obtained prepolymer in 15 minutes.:
Step 2: the prepolymer of step 1 gained had been not less than under 375 ℃ the temperature condition thermal treatment 8 hours, the cured article of the bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments (n=6) of acquisition.
This resin cured matter is at 1010cm
-1(phthalocyanine ring); 1360cm
-1And 1520cm
-1(triazine ring); 1246,1208cm
-1(Ar-O-Ar); 832,782,729cm
-1(phenyl ring) locates all to have occurred charateristic avsorption band, shows the bisphenol A-type bi-phthalonitrile resin cured article that has obtained containing aryl ether nitrile segments (n=6).According to the resin cured matter of this step preparation 375 ℃ handle 8h after, the temperature of decomposing 5% o'clock is 507 ℃; Carbon yield under 800 ℃ the nitrogen atmosphere is 71%.
Embodiment four
The present invention contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments (n=8) and the preparation of cured article thereof.
(1) contain bisphenol A-type bi-phthalonitrile resin synthetic of aryl ether nitrile segments (n=8):
Step 1: with dihydroxyphenyl propane, 2,6-dichlorobenzonitrile, Anhydrous potassium carbonate, N, dinethylformamide/toluene mixed solvent is added in the reaction vessel that has division box, is heated to 140 ℃ of back flow reaction 5 hours; Emit reaction generates in the water trap water byproduct and toluene then, continuing to heat up distills out toluene postcooling residual in the reaction system to room temperature.
Step 2: in the described reaction vessel that has a division box of step 1, add 4-nitro bi-phthalonitrile, 90 ℃ of reactions 10 hours.
Step 3: precipitate in the HCl solution with the reaction mixture impouring 0.1mol/L of step 2, filter, with a large amount of distilled water washs to neutral, oven dry is dry 12 hours in 90 ℃ of baking ovens, acquisition contains (n=8) bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments.
Wherein, dihydroxyphenyl propane, 2,6-dichlorobenzonitrile, Anhydrous potassium carbonate, N, the mole proportioning of dinethylformamide/toluene mixed solvent, 4-nitrophthalonitrile is:
| The repeated structural unit number | n＝8 |
| Dihydroxyphenyl propane | 0.5 |
| 2, the 6-dichlorobenzonitrile | 0.4 |
| The 4-nitrophthalonitrile | 0.2 |
| Anhydrous potassium carbonate | 0.55 |
| N, dinethylformamide/toluene mixed solvent | 5.0 |
The bisphenol A-type bi-phthalonitrile resin fusing point that contains aryl ether nitrile segments (n=8) that makes thus is 70 ℃, and solidifying summit temperature is 225 ℃.The infared spectrum of this resin is at 2967cm
-1(CH
3); 2231cm
-1(CN); 1246,1208cm
-1(Ar-O-Ar); 832,782,729cm
-1(phenyl ring) locates to have occurred charateristic avsorption band, shows the bisphenol A-type bi-phthalonitrile resin that has obtained containing aryl ether nitrile segments (n=8).
(2) contain the preparation of the bisphenol A-type bi-phthalonitrile resin cured article of aryl ether nitrile segments (n=8):
Step 1: will contain the bisphenol A-type bi-phthalonitrile resin and the cure-crosslinking agent 4 that is equivalent to its 5% quality of aryl ether nitrile segments (n=8), 4 '-diaminodiphenylsulfone(DDS) (DDS) mixes, and 220～240 ℃ of following Procuring obtained prepolymer in 15 minutes;
Step 2: the prepolymer of step 1 gained had been not less than under 375 ℃ the temperature condition thermal treatment 8 hours, the cured article of (n=8) bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments of acquisition.
This resin cured matter is at 1010cm
-1(phthalocyanine ring); 1360cm
-1And 1520cm
-1(triazine ring); 1246,1208cm
-1(Ar-O-Ar); 832,782,729cm
-1(phenyl ring) locates all to have occurred charateristic avsorption band, shows (n=8) bisphenol A-type bi-phthalonitrile resin cured article that has obtained containing aryl ether nitrile segments.According to the resin cured matter of this step preparation 375 ℃ handle 8h after, the temperature of decomposing 5% o'clock is 500 ℃; Carbon yield under 800 ℃ the nitrogen atmosphere is 66%.
Execute mode as can be seen by the above-mentioned fact: the biphenyl type that contains aryl ether nitrile segments and the bisphenol A-type bis-phthalonitrile monomer of the present invention's preparation have low melting point, wide processing temperature window, fusing point peak on the DSC spectrogram appears at 50-70 ℃, and curing exothermic peak appears at 223-240 ℃.Under 800 ℃ nitrogen atmosphere, decompose 5% temperature 500-560 ℃; The thermolysis carbon yield surpasses 66%.Thereby the bi-phthalonitrile resin that synthetic contains aryl ether nitrile segments has significantly been widened the process window of bi-phthalonitrile, has improved its processibility.The bi-phthalonitrile cured article of Huo Deing had both improved traditional narrow shortcoming of bi-phthalonitrile process window by this method, and thermotolerance is also kept simultaneously.These bi-phthalonitrile resins can be used for fields such as Aeronautics and Astronautics, naval vessel and prepare matrix material, can be used for electronic applications again and prepare insulating material, caking agent, electronic package material; Can also be used for matrix material that mechanical manufacturing field prepares high strength and modulus, caking agent etc.These materials all have good market outlook.
Claims (4)
1. bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments, its structural formula is:
N=2 wherein, 4,6 or 8.
2. preparation method who contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments may further comprise the steps:
Step 1: with dihydroxyphenyl propane, 2,6-dichlorobenzonitrile, catalyzer, solvent add and have in the reaction vessel of division box, are heated to 130～160 ℃ of following back flow reaction 3～6 hours; Emit reaction generates in the water trap water byproduct and toluene then, continuing to heat up distills out toluene postcooling residual in the reaction system to room temperature;
Step 2: in the described reaction vessel that has a division box of step 1, add 4-nitro bi-phthalonitrile, 80～100 ℃ of reactions 5～-10 hours down;
Step 3: with precipitation in the HCl solution of the reaction mixture impouring 0.1mol/L of step 2, filter, with a large amount of distilled water washs to neutral, thorough drying, acquisition contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments, its structural formula is
N=2 wherein, 4,6 or 8;
Wherein, dihydroxyphenyl propane, 2, the mole proportioning of 6-dichlorobenzonitrile, catalyzer, solvent, 4-nitrophthalonitrile is:
Described catalyzer is Anhydrous potassium carbonate or anhydrous sodium carbonate, and described solvent is 5: 1 the intensive polar solvent and the mixed solution of toluene for the mole proportioning, and wherein intensive polar solvent is N-Methyl pyrrolidone or N, dinethylformamide.
3. a cured article that contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments is the polymkeric substance that contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments, and its structure is the reticulated structure that comprises π-pi-conjugated phthalocyanine ring and triazine ring;
The described structural formula that contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments is:
N=2 wherein, 4,6 or 8;
The structural formula of described phthalocyanine ring is:
The structural formula of described triazine ring is:
4. the preparation method of the cured article of a bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments may further comprise the steps:
Step 1: the bisphenol A-type bi-phthalonitrile resin that will contain aryl ether nitrile segments mixes with the cure-crosslinking agent that is equivalent to its 5% quality, and 220～240 ℃ of following Procuring reactions 10～20 minutes, obtains prepolymer;
Step 2: the prepolymer of step 1 gained was heat-treated the cured article of the bisphenol A-type bi-phthalonitrile resin that contains aryl ether nitrile segments of acquisition 8～12 hours being not less than under 375 ℃ the temperature condition;
Wherein: the described structural formula that contains the bisphenol A-type bi-phthalonitrile resin of aryl ether nitrile segments is:
N=2 wherein, 4,6 or 8; Described cure-crosslinking agent is: 2,6-two-4-amino-benzene oxygen cyanobenzene, 4,4 '-diaminodiphenylsulfone(DDS), 1,3-two-3-amino-benzene oxygen benzene, 1, any one in 4-two-4-amino-benzene oxygen benzene, 3-amino-benzene oxygen-4-phenyl two sulfones or 4-amino-benzene oxygen-4-phenyl two sulfones.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102272271A CN101914038A (en) | 2010-07-15 | 2010-07-15 | Bisphenol A type bis-phthalonitrile resin with aryl ether nitrile segments, cured product and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102272271A CN101914038A (en) | 2010-07-15 | 2010-07-15 | Bisphenol A type bis-phthalonitrile resin with aryl ether nitrile segments, cured product and preparation method thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103811907A Division CN102887999A (en) | 2010-07-15 | 2010-07-15 | Bisphenol A bisphthalonitrile resin containing arylethernitrile chain segment, cured resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101914038A true CN101914038A (en) | 2010-12-15 |
Family
ID=43321717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102272271A Pending CN101914038A (en) | 2010-07-15 | 2010-07-15 | Bisphenol A type bis-phthalonitrile resin with aryl ether nitrile segments, cured product and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101914038A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936466A (en) * | 2012-11-28 | 2013-02-20 | 黑龙江省科学院石油化学研究院 | Modified bisphthalonitrile resin structure glue film and preparation method thereof |
| CN103172858A (en) * | 2013-04-24 | 2013-06-26 | 苏州益可泰电子材料有限公司 | Preparation method of electronic material for transmitting high-frequency signals |
| CN103260344A (en) * | 2013-04-24 | 2013-08-21 | 苏州益可泰电子材料有限公司 | Signal transmission electronic circuit of non-linear editing system |
| CN105061262A (en) * | 2015-08-24 | 2015-11-18 | 广东顺德高耐特新材料有限公司 | Low-melting-point aromatic-nitrile-group resin monomer and preparation thereof and aromatic-nitrile-group polymer and preparation method thereof |
| CN106046360A (en) * | 2016-04-15 | 2016-10-26 | 电子科技大学 | Aromatic nitrile polymer and preparation method thereof |
| CN106589349A (en) * | 2016-11-03 | 2017-04-26 | 大连理工大学 | Bisphthalonitrile resin with main chain containing triaryl-s-triazine structure, and preparation method thereof |
| CN106700419A (en) * | 2013-10-18 | 2017-05-24 | 柯礼军 | Plastic manufacture method |
| CN109096753A (en) * | 2017-06-21 | 2018-12-28 | 中国人民解放军国防科学技术大学 | Nitrile resin composite material and preparation method thereof |
| CN109608489A (en) * | 2018-12-12 | 2019-04-12 | 中国科学院化学研究所 | The phthalonitrile-terminated siliceous poly (arylene ether nitrile) oligomer of one kind, its solidfied material and the preparation method and application thereof |
| CN109705072A (en) * | 2018-12-12 | 2019-05-03 | 中国科学院化学研究所 | A kind of phthalonitrile oligomer, its solidfied material and its preparation method and application |
| CN111875794A (en) * | 2020-07-31 | 2020-11-03 | 成都大学 | Novel preparation method of nitrile resin monomer |
| CN113388137A (en) * | 2021-05-21 | 2021-09-14 | 电子科技大学 | Preparation method of high-strength high-temperature-resistant poly (arylene ether nitrile) film |
| CN114506098A (en) * | 2022-02-24 | 2022-05-17 | 四川金象赛瑞化工股份有限公司 | Resin-based fiber reinforced composite material for copper-clad plate and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050277A (en) * | 2006-06-30 | 2007-10-10 | 电子科技大学 | Copolymer of polyarylether nitrile containing chian element of iso-benzene and preparation method |
| CN101555348A (en) * | 2009-04-30 | 2009-10-14 | 电子科技大学 | Composite material of polycarylene ether nitrile fiberglass and preparation method thereof |
-
2010
- 2010-07-15 CN CN2010102272271A patent/CN101914038A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050277A (en) * | 2006-06-30 | 2007-10-10 | 电子科技大学 | Copolymer of polyarylether nitrile containing chian element of iso-benzene and preparation method |
| CN101555348A (en) * | 2009-04-30 | 2009-10-14 | 电子科技大学 | Composite material of polycarylene ether nitrile fiberglass and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| RONGHUA DU,ET AL.: "Synthesis and thermal properties of bisphthalonitriles containing aromatic ether nitrile linkages", 《POLYMER DEGRADATION AND STABILITY》 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936466A (en) * | 2012-11-28 | 2013-02-20 | 黑龙江省科学院石油化学研究院 | Modified bisphthalonitrile resin structure glue film and preparation method thereof |
| CN102936466B (en) * | 2012-11-28 | 2013-12-25 | 黑龙江省科学院石油化学研究院 | Modified bisphthalonitrile resin structure glue film and preparation method thereof |
| CN103172858A (en) * | 2013-04-24 | 2013-06-26 | 苏州益可泰电子材料有限公司 | Preparation method of electronic material for transmitting high-frequency signals |
| CN103260344A (en) * | 2013-04-24 | 2013-08-21 | 苏州益可泰电子材料有限公司 | Signal transmission electronic circuit of non-linear editing system |
| CN103172858B (en) * | 2013-04-24 | 2015-05-20 | 苏州益可泰电子材料有限公司 | Preparation method of electronic material for transmitting high-frequency signals |
| CN103260344B (en) * | 2013-04-24 | 2015-09-30 | 苏州益可泰电子材料有限公司 | A kind of nonlinear editing system Signal transmissions electronic circuit |
| CN106700419A (en) * | 2013-10-18 | 2017-05-24 | 柯礼军 | Plastic manufacture method |
| CN105061262A (en) * | 2015-08-24 | 2015-11-18 | 广东顺德高耐特新材料有限公司 | Low-melting-point aromatic-nitrile-group resin monomer and preparation thereof and aromatic-nitrile-group polymer and preparation method thereof |
| CN106046360A (en) * | 2016-04-15 | 2016-10-26 | 电子科技大学 | Aromatic nitrile polymer and preparation method thereof |
| CN106589349A (en) * | 2016-11-03 | 2017-04-26 | 大连理工大学 | Bisphthalonitrile resin with main chain containing triaryl-s-triazine structure, and preparation method thereof |
| CN109096753A (en) * | 2017-06-21 | 2018-12-28 | 中国人民解放军国防科学技术大学 | Nitrile resin composite material and preparation method thereof |
| CN109096753B (en) * | 2017-06-21 | 2021-02-23 | 中国人民解放军国防科学技术大学 | Nitrile resin composite material and preparation method thereof |
| CN109608489A (en) * | 2018-12-12 | 2019-04-12 | 中国科学院化学研究所 | The phthalonitrile-terminated siliceous poly (arylene ether nitrile) oligomer of one kind, its solidfied material and the preparation method and application thereof |
| CN109705072A (en) * | 2018-12-12 | 2019-05-03 | 中国科学院化学研究所 | A kind of phthalonitrile oligomer, its solidfied material and its preparation method and application |
| CN109608489B (en) * | 2018-12-12 | 2020-07-14 | 中国科学院化学研究所 | Phthalonitrile-terminated silicon-containing poly (arylene ether nitrile) oligomer, cured product thereof, and preparation method and application thereof |
| CN109705072B (en) * | 2018-12-12 | 2020-08-21 | 中国科学院化学研究所 | Phthalonitrile oligomer, condensate thereof, and preparation method and application thereof |
| CN111875794A (en) * | 2020-07-31 | 2020-11-03 | 成都大学 | Novel preparation method of nitrile resin monomer |
| CN113388137A (en) * | 2021-05-21 | 2021-09-14 | 电子科技大学 | Preparation method of high-strength high-temperature-resistant poly (arylene ether nitrile) film |
| CN113388137B (en) * | 2021-05-21 | 2022-04-15 | 电子科技大学 | Preparation method of high-strength high-temperature-resistant poly (arylene ether nitrile) film |
| CN114506098A (en) * | 2022-02-24 | 2022-05-17 | 四川金象赛瑞化工股份有限公司 | Resin-based fiber reinforced composite material for copper-clad plate and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101914038A (en) | Bisphenol A type bis-phthalonitrile resin with aryl ether nitrile segments, cured product and preparation method thereof | |
| KR101922791B1 (en) | A quick responsive, shape memory thermoset polyimide and preparation method thereof | |
| Laskoski et al. | Improved synthesis and properties of aryl ether-based oligomeric phthalonitrile resins and polymers | |
| CN102976972A (en) | Nitrile resin monomer, nitrile resin polymer and preparation method of nitrile resin monomer and nitrile resin polymer | |
| CN102887999A (en) | Bisphenol A bisphthalonitrile resin containing arylethernitrile chain segment, cured resin and preparation method thereof | |
| CN100554246C (en) | Double end group ortho-benzene dimethyl nitrile-benzo oxazine resin, cured article and its production and use | |
| CN101619131B (en) | O-phthalodinitrile end-blocked soluble polyarylether resin with phthalazinone structure and condensate and preparation method thereof | |
| CN103664699B (en) | Autocatalytic nitrile resin monomer, polymer and preparation method of polymer | |
| Saxena et al. | Synthesis and properties of polyarylene ether nitrile copolymers | |
| CN100558716C (en) | Benzoxazine colophony intermediate and its production and use | |
| CN102504252B (en) | Amino phenoxy phthalonitrile pre-polymer, condensate and preparation method and application thereof | |
| CN102120820B (en) | A kind of method of performing aqueous synthesis of thermosetting polyimide | |
| EP3279232A1 (en) | Cyanic acid ester compound, curable resin composition containing said compound, and cured object obtained therefrom | |
| CN103289089B (en) | Method for preparing triple phenol type poly-phthalonitrile resin with alkyl center | |
| CN103739519A (en) | Low-viscosity nitrile resin monomer, copolymer, cured material and preparation method thereof | |
| CN104130409B (en) | A kind of preparation method of phenolphthalein type polyimides | |
| CN103694191A (en) | Polyfunctional group nitrile resin monomer and polymer and preparation method thereof | |
| CN103408755A (en) | Low-viscosity cyano resin monomer and polymer, and preparation method thereof | |
| CN102702521B (en) | Macromolecule triazine charring agent with main chain containing piperazidine structure, and preparation method thereof | |
| CN102875800A (en) | Phenolphthalein polyarylether ketone copolymer and preparation method thereof | |
| CN102964594B (en) | Method for preparing naphthyl polystyrene nitrile resin | |
| CN105061262A (en) | Low-melting-point aromatic-nitrile-group resin monomer and preparation thereof and aromatic-nitrile-group polymer and preparation method thereof | |
| CN108129640A (en) | A kind of heat-resistant fireproof epoxy curing agent and preparation method thereof | |
| CN102702522B (en) | Macromolecule triazine charring agent and preparation method thereof | |
| CN113402423B (en) | Phthalonitrile monomer containing parylene structure, phthalonitrile resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20101215 |