CN105037721B - Application of active-hydrogen-containing heterocyclic compound to preparation of phthalonitrile resin - Google Patents
Application of active-hydrogen-containing heterocyclic compound to preparation of phthalonitrile resin Download PDFInfo
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Abstract
The invention provides application of an active-hydrogen-containing heterocyclic compound to preparation of phthalonitrile resin. The active-hydrogen-containing heterocyclic compound is one of active-hydrogen-containing carbazole, active-hydrogen-containing imidazole, active-hydrogen-containing pyrimidine, active-hydrogen-containing purine, active-hydrogen-containing piperazine, active-hydrogen-containing pyrrole, active-hydrogen-containing pyrazole, active-hydrogen-containing indazole, active-hydrogen-containing indole, active-hydrogen-containing pyrrolo-pyridine and active-hydrogen-containing phthalazinone. According to the new application of the active-hydrogen-containing heterocyclic compound, namely application of the active-hydrogen-containing heterocyclic compound to preparation of phthalonitrile resin, provided by the invention, the active-hydrogen-containing heterocyclic compound is used as a curing agent to accelerate curing of phthalonitrile resin, and meanwhile, heat stability and heat oxygen stability of phthalonitrile resin are improved.
Description
Technical field
The invention belongs to processing of high molecular material technical field, more particularly to heterocyclic compound containing reactive hydrogen are preparing adjacent benzene
Application in dimethoxy nitrile resin.
Background technology
Heterocyclic compound (heterocyclic compound) refers to the class compound with circulus.Constitute ring
Atom carbon atom outside, also at least contain a hetero atom (non-carbon), hetero atom includes oxygen, sulfur, nitrogen etc..Heterocyclic compound
Thing is prevalent among the structure of drug molecule, and it is heterocyclic compound that the important compound relevant with biology is most, for example
Nucleic acid, some vitamin, antibiotic, hormone, pigment and alkaloid etc., are used as medicine more these heterocyclic compounds.Also close at present
Into varied heterocyclic compound with various performances, medicine, Insecticides (tech) ＆ Herbicides (tech), dyestuff, plastics etc. can be made.Additionally,
Heterocyclic compound be used to prepare high performance resin by excellent heat and thermo-oxidative stability often as raw material, and such as polyamides is sub-
Amine, polybenzimidazoles etc..Heterocyclic compound containing reactive hydrogen is the heterocyclic compound that finger ring up to has less-NH- a structure.Mesh
It is front and have no document or research and propose heterocyclic compound containing reactive hydrogen as firming agent to accelerate o-phthalonitrile resin to solidify.
Firming agent is added to a certain extent to improve the curing rate of o-phthalonitrile resin, while reducing its solidified bars
Part.Primary aromatic amine, organic acid, organic acid/ammonium salt and slaine, phenols or amine curing agent etc. can effectively accelerate neighbour
The solidification of phthalonitrile resin.But above-mentioned firming agent have the shortcomings that one it is fatal：O-phthalonitrile resin is as resistance to height
The high temperature for usually needing long-time to tolerate more than 300 DEG C when adiabator is used, and amine and other firming agent are in such high temperature
Under heat stability and thermo-oxidative stability it is not good, this can reduce the performance of resin.
The content of the invention
It is an object of the invention to provide the new application containing reactive hydrogen heterocyclic compound, that is, preparing o-phthalonitrile resin
In application, reactive hydrogen heterocyclic compound will be contained and accelerate o-phthalonitrile resin solidification as firming agent, and improve O-phthalic
The heat stability and thermo-oxidative stability of nitrile resin.
The present invention is provided and confirms that heterocyclic compound containing reactive hydrogen can speed up o-phthalonitrile resin solidification, can conduct
The firming agent of o-phthalonitrile resin, applies in o-phthalonitrile resin is prepared.
Application of the above-mentioned heterocyclic compound containing reactive hydrogen in o-phthalonitrile resin is prepared, the jeterocyclic chemistry containing reactive hydrogen
Compound be carbazole containing reactive hydrogen, imidazoles containing reactive hydrogen, pyrimidine containing reactive hydrogen, purine containing reactive hydrogen, piperazine containing reactive hydrogen, containing activity
Hydrogen pyrroles, pyrazoles containing reactive hydrogen, containing active hydrogen indazole, containing active hydrogen indoles, pyrrolopyridine containing reactive hydrogen, phenodiazine containing reactive hydrogen
One kind in miscellaneous naphthalenone, their structural formula is as follows：
Carbazole containing reactive hydrogen：
Imidazoles containing reactive hydrogen：
Pyrimidine containing reactive hydrogen：
Purine containing reactive hydrogen：
Piperazine containing reactive hydrogen：
Pyrroles containing reactive hydrogen：
Pyrazoles containing reactive hydrogen：
Containing active hydrogen indazole：
Containing active hydrogen indoles：
Pyrrolopyridine containing reactive hydrogen：
Phthalazone containing reactive hydrogen：
In structure above, wave is referred to herein can be by covalent bond and other atoms, functional group or macromolecular main chain
It is connected.
Application of the above-mentioned heterocyclic compound containing reactive hydrogen in o-phthalonitrile resin is prepared, can pass through following processing step
Realize：
(1) melt blending
It is 100 according to phthalonitrile and the mass ratio containing reactive hydrogen heterocyclic compound：(2~100) dispensing；
Under agitation phthalonitrile is heated to into molten condition, then is added containing reactive hydrogen in the phthalonitrile of melting
Heterocyclic compound and mix homogeneously, stop heating simultaneously natural after phthalonitrile and the mix homogeneously of heterocyclic compound containing reactive hydrogen
Room temperature is cooled to, then phthalonitrile and blend containing reactive hydrogen heterocyclic compound granule or powder is ground into into；
(2) solidification of blend
By step (1) gained granule or powder blend under nitrogen atmosphere or oxygen atmosphere successively according to temperature below
Solidified with temperature retention time：0.0~5.0 hour is incubated at 280 DEG C of 220 DEG C≤T ＜；0.5 is incubated at 370 DEG C of 280 DEG C≤T ＜
~24.0 hours；0~24.0 hour is incubated at 370 DEG C≤T≤400 DEG C；Solidification cools to room temperature with the furnace and obtains final product adjacent benzene after terminating
Dimethoxy nitrile resin.
Heretofore described phthalonitrile refers to the compound of phthalonitrile group, and general structure is as follows：
In formula, R1, R2, R3, R4Can be alkyl, phenyl, hydrogen atom or halogen atom.
Compared with prior art, the invention has the advantages that：
1st, the present invention has excavated new purposes for known compound heterocyclic compound containing reactive hydrogen, that is, accelerate phthalonitrile
Resin solidification, can serve as the firming agent of o-phthalonitrile resin, open up the new application of heterocyclic compound containing reactive hydrogen.
2nd, the present invention will contain reactive hydrogen heterocyclic compound as firming agent, and with phthalonitrile blending O-phthalic is prepared
Nitrile resin, using heterocyclic compound containing reactive hydrogen the solidification of o-phthalonitrile resin can be accelerated, and significantly improve solidification rate (see figure
2).Simultaneously because the good heat stability of heterocyclic compound containing reactive hydrogen, is difficult at high temperature volatilization and decomposes, neighbour can be prevented effectively from
Phthalonitrile resin is during solidification and use due to the relatively low and caused o-phthalonitrile resin of the thermostability of firming agent
Mechanical performance and hot property are reduced, so as to improve the heat stability and thermo-oxidative stability of o-phthalonitrile resin.From embodiment
Understand, the T5% of obtained o-phthalonitrile resin more than 480 DEG C, carbon yield also above 72%, with add arylamine class or
Phenols curing agent is compared, and the heat stability and thermo-oxidative stability of o-phthalonitrile resin obtain a certain degree of raising.
3rd, it is of the present invention to accelerate o-phthalonitrile resin solidification, equipment to set for conventional using heterocyclic compound containing reactive hydrogen
It is standby, thus it is easy to industrialized production.
Description of the drawings
Fig. 1 is the infrared spectrum in embodiment 1 before and after blend solidification.
Fig. 2 is the rheological curve figure of blend and phthalonitrile monomer 1 in 325 DEG C of isothermal cures in embodiment 1.
Fig. 3 is that the TGA curves in embodiment 1 before and after blend solidification (in 10 DEG C/min of heating rate, are surveyed under nitrogen atmosphere
).
Specific embodiment
Prepared by phthalonitrile tree to heterocyclic compound containing reactive hydrogen of the present invention below by specific embodiment
Application in fat is described further.
Embodiment 1
The present embodiment is that reactive hydrogen purine formation accelerates o-phthalonitrile resin：
(1) synthesis of the A1 of heterocyclic compound containing reactive hydrogen
Adenine (Cas is added in 100mL there-necked flasks：73-24-5,0.02mol, 2.70g), the refined NMP of 60ml, stirring
After 10 minutes, pyromellitic dianhydride (PMDA, 0.01mol, 2.18g) is added thereto to, after 7h is stirred at room temperature, in reaction system
20mL refined toluenes are added, and system temperature is risen to into 145 DEG C of backflow backflows, and react 7h at this temperature.Treat in system not
There is water to produce again, rise high-temperature to 180 DEG C, separate the toluene in system, when question response system temperature steeply rises, illustrate toluene
Remove substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and wash, the filter cake of filtration, then will filter
Cake is washed three times, and methanol is stirred to be washed twice, and after sucking filtration, filter cake is dried 12h for 70 DEG C in vacuum drying oven, obtains heterocyclic compound containing reactive hydrogen
Thing A1. reaction equations are as follows：
(2) synthesis of phthalonitrile monomer 1
Reference literature Teddy M.Keller, Dawn D.Dominguez, High temperature resorcinol-
Based phthalonitrile polymer, polymer, 2005,46,4614-4618.
(3) melt blending
5.0g phthalonitrile monomers 1 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A-45:20 add the 1.0g A6 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting, high
Fast mechanical agitation 4min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be blended
Thing；
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：275
2.0 hours are incubated at DEG C；2.0 hours are incubated at 325 DEG C；2.0 hours are incubated at 375 DEG C；Solidification cools to room with the furnace after terminating
Temperature.Infrared spectrum before and after blend solidification is shown in Fig. 1, and the rheological curve figure of isothermal cure is shown in Fig. 2, before and after blend solidification
TGA curves are shown in Fig. 3.
It can be seen from figure 1 that being mainly shown as compared with the IR characteristic peaks before blend solidification after blend solidification：Adjacent benzene two
The IR characteristic peak 2234cm of formonitrile HCN base-1Significantly weaken, illustrate that phthalonitrile groups have occurred and that reaction, blend has been consolidated
Change.
As can be seen from Figure 2, a small amount of monomer A1 of heterocyclic compound containing reactive hydrogen, the solidification speed of phthalonitrile monomer 1 be with the addition of
Rate is substantially accelerated, and illustrates that heterocyclic compound containing reactive hydrogen can accelerate o-phthalonitrile resin to solidify.
As can be seen from Figure 3, blend is cured, T after blend solidification5%For 489.74 DEG C, carbon yield is 73.69%, explanation
Obtained o-phthalonitrile resin has excellent heat stability.
Embodiment 2
The present embodiment is that imidazoles accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A2 of heterocyclic compound containing reactive hydrogen
(Cas is added in 100mL there-necked flasks：4919-03-30.02mol, 1.66g), the refined NMP of 60ml, stir 10 points
Zhong Hou, is added thereto to 3,3,4,4- biphenyl dianhydrides (BPDA, 0.01mol, 2.94g), after 7h is stirred at room temperature, in reaction system
20mL refined toluenes are added, and system temperature is risen to into 145 DEG C of backflows, and react 5h at this temperature.Treat to be there is no longer in system
Water is produced, and rises high-temperature to 180 DEG C, separates the toluene in system, when question response system temperature steeply rises, illustrates toluene
Basic removing, closes heating and stirs, and the system for the treatment of is down to room temperature, with hot water precipitation, stirs and wash, the filter cake of filtration, then by filter cake water
Wash three times, methanol is stirred to be washed twice, after sucking filtration, filter cake is dried 12h for 70 DEG C in vacuum drying oven, obtains heterocyclic compound containing reactive hydrogen
A2.
(2) synthesis of phthalonitrile monomer 2
Synthesize according to documents below methods described：D.Kumar,U.Razdan and A.D.Gupta,Thermally
polymerizable bisaryloxy-bisimido-bisphthalonitriles containing
dimethylsilane,hexafluoroisopropylidene,ether,and keto groups:Synthesis,
characterization,and NMR study,31,1993,2319-2331.
Gained phthalonitrile monomer 2 structural formula be：
(3) melt blending
5.0g phthalonitrile monomers 2 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A2:20 add the 1.0g A2 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting, high
Fast mechanical agitation 2min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be blended
Thing.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：260
4.0 hours are incubated at DEG C；12.0 hours are incubated at 330 DEG C；2.0 hours are incubated at 390 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 494.37 DEG C, carbon yield is 72.63%.
Embodiment 3
The present embodiment can speed up o-phthalonitrile resin solidification for pyrimidine：
(1) synthesis of the A3 of heterocyclic compound containing reactive hydrogen
ODPA (0.10mol, 31.02g), 124ml NMP are added in 500ml there-necked flasks, oil bath is warming up to ODPA can be complete
CL (temperature is about 70 DEG C, and now system is in light yellow clear), then cool the temperature to room temperature.At room temperature in reactant liquor
Add cytosine (Cas：71-30-7,0.20mol, 22.22g), after 6h is stirred at room temperature.Addition acetic acid pyrimidine acid anhydride (0.60mol,
62.19g, 98.5%wt) and pyridine (0.60mol, 47.70g, 99.5%wt), and system temperature is risen to into 120 DEG C, and here
At a temperature of react 3h.But system is down to room temperature, with hot water precipitation, stirs and wash, the filter cake of filtration, then filter cake is washed three times, methanol
Stir and wash twice, after sucking filtration, filter cake is dried 12h for 70 DEG C in vacuum drying oven, obtains the A3 of heterocyclic compound containing reactive hydrogen.
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2.
(3) melt blending
5.0g phthalonitrile monomers 2 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A-13:5 add the 0.25g A3 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting, high
Fast mechanical agitation 2.5min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be total to
Mixed thing.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：260
4.0 hours are incubated at DEG C；10.0 hours are incubated at 350 DEG C；3.0 hours are incubated at 380 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 505.33 DEG C, carbon yield is 78.19%.
Embodiment 4
The present embodiment is that pyrimidine accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A4 of heterocyclic compound containing reactive hydrogen
3,3,4,4- biphenyl dianhydrides (BPDA, 0.11mol, 32.36g), 132ml NMP are added in 500ml there-necked flasks, oil
Bath is warming up to BPDA and can be completely dissolved (temperature is about 70 DEG C, and now system is in light yellow clear), then cools the temperature to room temperature.
6- amino-uracils (0.22mol, 28.41g) are added in reactant liquor under room temperature, after 5h is stirred at room temperature.Add acetic anhydride
(0.66mol, 68.41g, 98.5%wt) and pyridine (0.66mol, 52.47g, 99.5%wt), and system temperature is risen to into 130
DEG C, and 4h is reacted at this temperature.But system is down to room temperature, with hot water precipitation, stirs and wash, the filter cake of filtration, then filter cake is washed
Three times, methanol is stirred to be washed twice, and after sucking filtration, filter cake is dried 12h for 70 DEG C in vacuum drying oven, obtains the A4. of heterocyclic compound containing reactive hydrogen
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2
(3) melt blending
5.0g phthalonitrile monomers 2 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A4:15 add the 0.75g A4 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting,
High speed machine stirs 3min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be total to
Mixed thing；
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：260
4.0 hours are incubated at DEG C；12.0 hours are incubated at 340 DEG C；4.0 hours are incubated at 375 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 495.33 DEG C, carbon yield is 72.57%.
Embodiment 5
The present embodiment is that carbazole accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A5 of heterocyclic compound containing reactive hydrogen
Synthesize according to documents below methods described:Yu Chen,Dandan Han,Tao Wang,and Xiuyan Li,
Efficient Synthesis of Arylated Carbazole from Cyclopentadienyliron
Complexes,Ind.Eng.Chem.Res.2013,52,3646-3652.
(2) synthesis of phthalonitrile monomer 2 is referring to embodiment 2
(3) melt blending
5.0g phthalonitrile monomers 2 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A1:10 add the 0.5g A1 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting, high
Fast mechanical agitation 3min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be blended
Thing.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：270
3.0 hours are incubated at DEG C；20.0 hours are incubated at 340 DEG C；4.0 hours are incubated at 390 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained phthalonitrile5%For 500.37 DEG C, carbon yield is 76.73%.
Embodiment 6
The present embodiment can speed up o-phthalonitrile resin solidification for isoquinolin：
(1) synthesis of the A6 of heterocyclic compound containing reactive hydrogen
(2H) -one (Cas of 6- aminoisoquinolines -1 is added in 100mL there-necked flasks：216099-46-6,0.02mol,
1.73g), the refined NMP of 60ml, after stirring 10 minutes, are added thereto to pyromellitic acid dianhydride (PMDA, 0.01mol, 2.94g), room
After temperature stirring 5h, 20mL refined toluenes are added in reaction system, and system temperature is risen to into 145 DEG C of backflows, and in this temperature
Lower reaction 7h.Treat to there is no longer water generation in system, rise high-temperature to 180 DEG C, separate the toluene in system, question response system temperature
When steeply rising, illustrate that toluene is removed substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, is stirred
Wash, the filter cake of filtration, then filter cake is washed three times, methanol is stirred to be washed twice, after sucking filtration, filter cake 70 DEG C of dryings in vacuum drying oven
12h, obtains the A6. of heterocyclic compound containing reactive hydrogen
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1.
(3) solution blending
5.0g phthalonitrile monomers 1 are added in 100mL tetrahydrofuran solutions, treats that phthalonitrile monomer is completely dissolved
Afterwards, the 0.5g A6 of heterocyclic compound containing reactive hydrogen are added in solution, after A6 dissolvings, dried powder is filled in 45 DEG C of dryings of pressurizeing
Divide grinding, that is, obtain the blend of phthalonitrile and A7.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：240
3.0 hours are incubated at DEG C；18.0 hours are incubated at 340 DEG C；5.0 hours are incubated at 390 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 500.37 DEG C, carbon yield is 76.72%.
Embodiment 7
The present embodiment is that purine accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A7 of heterocyclic compound containing reactive hydrogen
3,3,4,4- biphenyl dianhydrides (BPDA, 0.11mol, 32.36g), 132ml NMP are added in 500ml there-necked flasks, oil
Bath is warming up to PMDA and can be completely dissolved (temperature is about 70 DEG C, and now system is in light yellow clear), then cools the temperature to room temperature.
Under room temperature in reactant liquor add 6- amino -7- azapurine (Cas：1500-85-20.22mol, 29.51g), 5h is stirred at room temperature
Afterwards.Add acetic anhydride (0.66mol, 68.41g, 98.5%wt) and pyridine (0.66mol, 52.47g, 99.5%wt), and by body
It is that temperature rises to 130 DEG C, and reacts 4h at this temperature.But system is down to room temperature, with hot water precipitation, stirs and wash, the filter of filtration
Cake, then filter cake is washed three times, methanol is stirred to be washed twice, and after sucking filtration, filter cake is dried 12h for 70 DEG C in vacuum drying oven, is obtained containing activity
Hydrogen heterocyclic compound A7.
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2
(3) melt blending
5.0g phthalonitrile monomers 2 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A7:15 add the 0.75g A7 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting,
High speed machine stirs 3min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be total to
Mixed thing；
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：255
4.0 hours are incubated at DEG C；12.0 hours are incubated at 335 DEG C；4.0 hours are incubated at 380 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 488.14 DEG C, carbon yield is 74.22%.
Embodiment 8
The present embodiment is that purine accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A8 of heterocyclic compound containing reactive hydrogen
3,3,4,4- biphenyl dianhydrides (BPDA, 0.11mol, 32.36g), 132ml NMP are added in 500ml there-necked flasks, oil
Bath is warming up to PMDA and can be completely dissolved (temperature is about 70 DEG C, and now system is in light yellow clear), then cools the temperature to room temperature.
The miscellaneous nitrogen adenine (Cas of 8- are added in reactant liquor under room temperature：1123-54-20.22mol, 29.94g), after 5h is stirred at room temperature.Plus
Enter acetic anhydride (0.66mol, 68.41g, 98.5%wt) and pyridine (0.66mol, 52.47g, 99.5%wt), and by system temperature
130 DEG C are risen to, and reacts 4h at this temperature.But system is down to room temperature, with hot water precipitation, stirs and wash, the filter cake of filtration, then will filter
Cake is washed three times, and methanol is stirred to be washed twice, and after sucking filtration, filter cake is dried 12h for 70 DEG C in vacuum drying oven, obtains heterocyclic compound containing reactive hydrogen
Thing A8.
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) melt blending
5.0g phthalonitrile monomers 1 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A-28:15 add the 0.75g A8 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting,
High speed machine stirs 3min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be total to
Mixed thing；
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：255
4.0 hours are incubated at DEG C；12.0 hours are incubated at 335 DEG C；4.0 hours are incubated at 380 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 497.14 DEG C, carbon yield is 74.22%.
Embodiment 9
The present embodiment is that piperazine accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A9 of heterocyclic compound containing reactive hydrogen
Synthesize according to documents below methods described:Maki Seki,Osamu Tsuruta,Yukio Aoyama,Aki
Soejima,Hiroshi Shimada,and Hikaru Nonaka,Synthesis and Pharmacological
Evaluation of 3-Amino-1-(5-indanyloxy)-2-propanol Derivatives as Potent
Sodium Channel Blockers for the Treatment of Stroke,Chem.Pharm.Bull.,2012,60
(4),488–498.
The structural formula of the A9 of heterocyclic compound containing reactive hydrogen is：
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1.
(3) melt blending
5.0g phthalonitrile monomers 1 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A9:5 add the 0.25g A9 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting, high
Fast mechanical agitation 1min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be blended
Thing；
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：260
4.0 hours are incubated at DEG C；12.0 hours are incubated at 330 DEG C；2.0 hours are incubated at 390 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 486.01 DEG C, carbon yield is 76.19%.
Embodiment 10
The present embodiment is that isoquinolines accelerate o-phthalonitrile resin solidification：
(1) synthesis of the A10 of heterocyclic compound containing reactive hydrogen
6- aminoisoquinoline ketone (Cas are added in 100mL there-necked flasks：22246-00-00.02mol, 3.24g), 60ml it is smart
NMP processed, after stirring 10 minutes, is added thereto to 3,3,4,4- biphenyl dianhydrides (BPDA, 0.01mol, 2.94g), and 5h is stirred at room temperature
Afterwards, 20mL refined toluenes are added in reaction system, and system temperature is risen to into 145 DEG C of backflows, and react 7h at this temperature.
Treat to there is no longer water generation in system, rise high-temperature to 180 DEG C, separate the toluene in system, question response system temperature steeply rises
When, illustrate that toluene is removed substantially, to close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and wash, filtration
Filter cake, then filter cake is washed three times, methanol is stirred to be washed twice, and after sucking filtration, filter cake is dried 12h for 70 DEG C in vacuum drying oven, is obtained containing work
Property hydrogen heterocyclic compound A10.Reaction equation is as follows：
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) solution blending
5.0g phthalonitrile monomers 1 are added in 100mL tetrahydrofuran solutions, treats that phthalonitrile monomer is completely dissolved
Afterwards, the 0.6g A10 of heterocyclic compound containing reactive hydrogen are added in solution, after A10 dissolvings, 45 DEG C of dryings of pressurizeing, by dried powder
It is fully ground, that is, obtains the blend of phthalonitrile and A10.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：270
3.0 hours are incubated at DEG C；18.0 hours are incubated at 340 DEG C；4.0 hours are incubated at 390 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 499.37 DEG C, carbon yield is 74.43%.
Embodiment 11
The present embodiment accelerates o-phthalonitrile resin to solidify for pyrroles：
(1) synthesis of the A11 of heterocyclic compound containing reactive hydrogen
3- pyrroles alkanamine (Cas is added in 100mL there-necked flasks：79286-79-60.02mol, 1.73g), 60ml refine
NMP, after stirring 10 minutes, is added thereto to 3,3,4,4- biphenyl dianhydrides (BPDA, 0.01mol, 2.94g), after 5h is stirred at room temperature,
20mL refined toluenes are added in reaction system, and system temperature is risen to into 145 DEG C of backflows, and react 5h at this temperature.Treat
Water generation is there is no longer in system, high-temperature is risen to 180 DEG C, the toluene in system is separated, when question response system temperature steeply rises,
Illustrate that toluene is removed substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and wash, the filter of filtration
Cake, then filter cake is washed three times, methanol is stirred to be washed twice, and after sucking filtration, filter cake is dried 12h for 70 DEG C in vacuum drying oven, is obtained containing activity
Hydrogen heterocyclic compound A11. reaction equations are as follows：
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) solution blending
5.0g phthalonitrile monomers 1 are added in 100mL tetrahydrofuran solutions, treats that phthalonitrile monomer is completely dissolved
Afterwards, the 0.5g A11 of heterocyclic compound containing reactive hydrogen are added in solution, after A11 dissolvings, 45 DEG C of dryings of pressurizeing, by dried powder
It is fully ground, that is, obtains the blend of phthalonitrile and A11.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：220
3.0 hours are incubated at DEG C；8.0 hours are incubated at 340 DEG C；5.0 hours are incubated at 370 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 499.31 DEG C, carbon yield is 74.12%.
Embodiment 12
The present embodiment is that pyrrolidone accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A12 of heterocyclic compound containing reactive hydrogen
4- amino -2-Pyrrolidone (CAS is added in 100mL there-necked flasks：88016-17-5,0.02mol, 2.00g),
60ml refines NMP, after stirring 10 minutes, is added thereto to 3,3,4,4- biphenyl dianhydrides (BPDA, 0.01mol, 2.94g), room temperature
After stirring 7h, 20mL refined toluenes are added in reaction system, and system temperature is risen to into 145 DEG C of backflows, and at this temperature
Reaction 5h.Treat to there is no longer water generation in system, rise high-temperature to 180 DEG C, separate the toluene in system, question response system temperature
When steeply rising, illustrate that toluene is removed substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, is stirred
Wash, the filter cake of filtration, then filter cake is washed three times, methanol is stirred to be washed twice, after sucking filtration, filter cake 70 DEG C of dryings in vacuum drying oven
12h, obtains the A12. reaction equations of heterocyclic compound containing reactive hydrogen as follows：
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) solution blending
5.0g phthalonitrile monomers 1 are added in 100mL tetrahydrofuran solutions, treats that phthalonitrile monomer is completely dissolved
Afterwards, the 0.3g A12 of heterocyclic compound containing reactive hydrogen are added in solution, after A12 dissolvings, 45 DEG C of dryings of pressurizeing, by dried powder
It is fully ground, that is, obtains the blend of phthalonitrile and A12.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：225
5.0 hours are incubated at DEG C；18.0 hours are incubated at 330 DEG C；5.0 hours are incubated at 375 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 501.11 DEG C, carbon yield is 79.72%.
Embodiment 13
The present embodiment is that pyrazoles accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A13 of heterocyclic compound containing reactive hydrogen
Resorcinol (0.08mol, 8.08g) and potassium carbonate (0.252mol, 36g) are added in 250mL three-necked bottles, then
160mL DMSO solutions are added thereto to, 10min is stirred under room temperature under nitrogen protective condition, be then added thereto to 4- nitro pyrroles
Azoles (Cas：2075-46-9,0.17mol, 19.22g), after solution stirs 48h at 20 DEG C, cooling pours reactant liquor into 500mL
Stir in hot water and wash, collected by suction filter cake, filter cake is rinsed to neutrality with a large amount of water, filter cake is washed with a small amount of ethanol (50mL), take out
Filter cake is collected in filter, and under vacuum condition, 70 DEG C are dried 24h, that is, obtain the A13 of heterocyclic compound containing reactive hydrogen.Reaction equation is as follows：
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2.
(3) solution blending
5.0g phthalonitrile monomers 2 are added in 100mL tetrahydrofuran solutions, treats that phthalonitrile monomer is completely dissolved
Afterwards, the 0.4g A13 of heterocyclic compound containing reactive hydrogen are added in solution, after A13 dissolvings, 45 DEG C of dryings of pressurizeing, by dried powder
It is fully ground, that is, obtains the blend of phthalonitrile and A13.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：230
5.0 hours are incubated at DEG C；17.0 hours are incubated at 340 DEG C；5.0 hours are incubated at 375 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 498.08 DEG C, carbon yield is 79.32%.
Embodiment 14
The present embodiment can speed up o-phthalonitrile resin solidification for indazole：
(1) synthesis of the A14 of heterocyclic compound containing reactive hydrogen
Resorcinol (0.08mol, 8.08g) and potassium carbonate (0.252mol, 36g) are added in 250mL three-necked bottles, then
160mL DMSO solutions are added thereto to, 10min is stirred under room temperature under nitrogen protective condition, be then added thereto to 6- nitro Yin
Azoles (Cas：7597-18-4,0.17mol, 27.73g), after solution stirs 48h at 20 DEG C, cooling pours reactant liquor into 500mL
Stir in hot water and wash, collected by suction filter cake, filter cake is rinsed to neutrality with a large amount of water, filter cake is washed with a small amount of ethanol (100mL), take out
Filter cake is collected in filter, and under vacuum condition, 70 DEG C are dried 24h, that is, obtain the A14 of heterocyclic compound containing reactive hydrogen.Reaction equation is as follows：
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2.
(3) solution blending
5.0g phthalonitrile monomers 2 are added in 100mL tetrahydrofuran solutions, treats that phthalonitrile monomer is completely dissolved
Afterwards, the 1.2g A14 of heterocyclic compound containing reactive hydrogen are added in solution, after A14 dissolvings, 45 DEG C of dryings of pressurizeing, by dried powder
It is fully ground, that is, obtains the blend of phthalonitrile and A14.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：230
5.0 hours are incubated at DEG C；24.0 hours are incubated at 340 DEG C；6.0 hours are incubated at 380 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 488.18 DEG C, carbon yield is 72.51%.
Embodiment 15
The present embodiment is that indoline accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A15 of heterocyclic compound containing reactive hydrogen
Resorcinol (0.08mol, 8.08g) and potassium carbonate (0.252mol, 36g) are added in 250mL three-necked bottles, then
160mL DMSO solutions are added thereto to, 10min is stirred under room temperature under nitrogen protective condition, be then added thereto to 6- nitro Yin
Diindyl quinoline (Cas：19727-83-4,0.16mol, 26.26g), after solution stirs 48h at 20 DEG C, reactant liquor is poured in cooling
Stir in 500mL hot water and wash, collected by suction filter cake, filter cake is rinsed to neutrality with a large amount of water, filter cake is washed with a small amount of ethanol (100mL)
Wash, collected by suction filter cake, under vacuum condition, 70 DEG C are dried 24h, that is, obtain the A15 of heterocyclic compound containing reactive hydrogen.
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) melt blending
5.0g phthalonitrile monomers 1 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A15:16 add the 0.8g A15 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting,
High speed machine stirs 2min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be total to
Mixed thing.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：260
1.0 hours are incubated at DEG C；14.0 hours are incubated at 330 DEG C；5.0 hours are incubated at 380 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 497.17 DEG C, carbon yield is 73.71%.
Embodiment 16
The present embodiment can speed up o-phthalonitrile resin solidification for indolone：
(1) synthesis of the A16 of heterocyclic compound containing reactive hydrogen
5- amino indole -2- ketone (Cas are added in 100mL there-necked flasks：20876-36-2,0.02mol, 2.96g), 60ml
Refined NMP, after stirring 10 minutes, is added thereto to pyromellitic dianhydride (PMDA, 0.01mol, 2.18g), after 7h is stirred at room temperature,
20mL refined toluenes are added in reaction system, and system temperature is risen to into 145 DEG C of backflows, and react 7h at this temperature.Treat
Water generation is there is no longer in system, high-temperature is risen to 180 DEG C, the toluene in system is separated, when question response system temperature steeply rises,
Illustrate that toluene is removed substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and wash, the filter of filtration
Cake, then filter cake is washed three times, methanol is stirred to be washed twice, and after sucking filtration, filter cake is dried 12h for 70 DEG C in vacuum drying oven, is obtained containing activity
Hydrogen heterocyclic compound A16. reaction equations are as follows：
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2.
(3) melt blending
5.0g phthalonitrile monomers 2 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A16:14 add the 0.7g A16 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting,
High speed machine stirs 3min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be total to
Mixed thing.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：260
1.0 hours are incubated at DEG C；14.0 hours are incubated at 330 DEG C；5.0 hours are incubated at 380 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 496.71 DEG C, carbon yield is 73.01%.
Embodiment 17
The present embodiment is that indole accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A17 of heterocyclic compound containing reactive hydrogen
Resorcinol (0.08mol, 8.08g) and potassium carbonate (0.252mol, 36g) are added in 250mL three-necked bottles, then
160mL DMSO solutions are added thereto to, 10min is stirred under room temperature under nitrogen protective condition, be then added thereto to 7- nitro Yin
Diindyl (Cas：6960-42-5,0.17mol, 27.55g), after solution stirs 48h at 20 DEG C, cooling pours reactant liquor into 500mL
Stir in hot water and wash, collected by suction filter cake, filter cake is rinsed to neutrality with a large amount of water, filter cake is washed with a small amount of ethanol (100mL), take out
Filter cake is collected in filter, and under vacuum condition, 70 DEG C are dried 24h, that is, obtain the A17 of heterocyclic compound containing reactive hydrogen.Reaction equation is as follows：
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1.
(3) melt blending
5.0g phthalonitrile monomers 1 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A17:10 add the 0.5g A17 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting,
High speed machine stirs 2min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be total to
Mixed thing.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：235
4.0 hours are incubated at DEG C；20.0 hours are incubated at 345 DEG C；6.0 hours are incubated at 380 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 484.43 DEG C, carbon yield is 75.33%.
Embodiment 18
The present embodiment is that pyrrolopyridine accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A18 of heterocyclic compound containing reactive hydrogen
5- amino -1H- pyrrolo-es [3,2-B] pyridine (Cas are added in 100mL there-necked flasks：207849-66-9,
0.02mol, 2.66g), the refined NMP of 60ml, after stirring 10 minutes, be added thereto to pyromellitic dianhydride (PMDA, 0.01mol,
2.18g), it is stirred at room temperature after 7h, 20mL refined toluenes is added in reaction system, and system temperature is risen to into 145 DEG C of backflows, and
7h is reacted at this temperature.Treat to there is no longer water generation in system, rise high-temperature to 180 DEG C, separate the toluene in system, question response
When system temperature steeply rises, illustrate that toluene is removed substantially, close heating and stir, the system for the treatment of is down to room temperature, uses hot water
Precipitation, stirs and washes, the filter cake of filtration, then filter cake is washed three times, and methanol is stirred to be washed twice, and after sucking filtration, filter cake is 70 in vacuum drying oven
DEG C 12h is dried, obtains the A18. reaction equations of heterocyclic compound containing reactive hydrogen as follows：
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2.
(3) melt blending
5.0g phthalonitrile monomers 2 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A18:20 add the 1.0g A18 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting,
High speed machine stirs 3min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be total to
Mixed thing.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：250
5.0 hours are incubated at DEG C；16.0 hours are incubated at 340 DEG C；2.0 hours are incubated at 380 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 488.26 DEG C, carbon yield is 70.78%.
Embodiment 19
The present embodiment is that pyrrolopyridine accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A19 of heterocyclic compound containing reactive hydrogen
7- amino -1H- pyrrolo-es [2,3-C] pyridine [3,2-B] pyridine (Cas are added in 100mL there-necked flasks：165669-
36-3,0.02mol, 2.66g), the refined NMP of 60ml, after stirring 10 minutes, be added thereto to pyromellitic dianhydride (PMDA,
0.01mol, 2.18g), after 7h is stirred at room temperature, 20mL refined toluenes are added in reaction system, and system temperature is risen to into 145
DEG C backflow, and reacts at this temperature 7h.Treat to there is no longer water generation in system, rise high-temperature to 180 DEG C, separate the first in system
Benzene, when question response system temperature steeply rises, illustrates that toluene is removed substantially, closes heating and stirs, and the system for the treatment of is down to room
Temperature, with hot water precipitation, stirs and washes, the filter cake of filtration, then filter cake is washed three times, and methanol is stirred to be washed twice, and after sucking filtration, filter cake is in vacuum
70 DEG C are dried 12h in baking oven, obtain the A19. reaction equations of heterocyclic compound containing reactive hydrogen as follows：
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) melt blending
5.0g phthalonitrile monomers 1 are heated to into molten condition, according to phthalonitrile monomer and heterocycle containing reactive hydrogen
The mass ratio 100 of compound A19:10 add the 0.5g A19 of heterocyclic compound containing reactive hydrogen in the phthalonitrile monomer of melting,
High speed machine stirs 2min, then stops heating, and naturally cooling to smash gained solid mortar after room temperature both must be total to
Mixed thing.
(4) solidification of blend
Step (3) gained blend is solidified according to temperature below and temperature retention time successively under nitrogen atmosphere：250
4.0 hours are incubated at DEG C；19.0 hours are incubated at 340 DEG C；3.0 hours are incubated at 380 DEG C；Solidification cools to room with the furnace after terminating
Temperature.
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 493.16 DEG C, carbon yield is 77.04%.
Embodiment 20
The present embodiment is that phthalazone accelerates o-phthalonitrile resin solidification：
(1) synthesis of the A20 of heterocyclic compound containing reactive hydrogen
Add in 250mL three-necked bottles 4- (4- hydroxy phenyls) -2,3-benzodiazine -1- ketone (0.09mol, 19.10g) and
Potassium carbonate (0.168mol, 24g), is then added thereto to 160mL DMSO solutions, stirs under room temperature under nitrogen protective condition
10min, is then added thereto to 4- nitrophthalonitriles (0.08mol, 13.85g), after solution stirs 48h at 20 DEG C, drop
Temperature, reactant liquor is poured into stir in 500mL hot water and is washed, and collected by suction filter cake, filter cake is rinsed to neutrality with a large amount of water, by filter cake with less
Amount ethanol (100mL) washing, collected by suction filter cake, under vacuum condition, 70 DEG C are dried 24h, that is, obtain heterocyclic compound containing reactive hydrogen
Thing A2, i.e. phthalonitrile monomer containing phthalazone.
Reaction equation is as follows：
(2) solidification of phthalonitrile monomer containing phthalazone
By step (1) the gained A20 of phthalonitrile monomer containing phthalazone under nitrogen atmosphere successively according to following temperature
Degree and temperature retention time are solidified：12.0 hours are incubated at 230 DEG C；12.0 hours are incubated at 340 DEG C；Insulation 5.0 is little at 375 DEG C
When；
In the present embodiment, blend solidification before and after infrared spectrum in O-phthalic itrile group IR characteristic peaks similar to Fig. 1,
The T of gained o-phthalonitrile resin5%For 498.08 DEG C, carbon yield is 73.72%.
Claims (1)
1. application of the heterocyclic compound containing reactive hydrogen in o-phthalonitrile resin is prepared, it is characterised in that described containing reactive hydrogen
Heterocyclic compound be carbazole containing reactive hydrogen, pyrimidine containing reactive hydrogen, purine containing reactive hydrogen, piperazine containing reactive hydrogen, pyrroles containing reactive hydrogen,
Pyrazoles containing reactive hydrogen, containing active hydrogen indazole, containing the one kind in active hydrogen indoles, pyrrolopyridine containing reactive hydrogen, their structure
Formula is as follows：
Carbazole containing reactive hydrogen：
Pyrimidine containing reactive hydrogen：
Purine containing reactive hydrogen：
Piperazine containing reactive hydrogen：
Pyrroles containing reactive hydrogen：
Pyrazoles containing reactive hydrogen：
Containing active hydrogen indazole：
Containing active hydrogen indoles：
Pyrrolopyridine containing reactive hydrogen：
In structure above, wave referred to and can be connected with other atoms, functional group or macromolecular main chain by covalent bond herein,
Application of the heterocyclic compound containing reactive hydrogen in o-phthalonitrile resin is prepared, is realized by following processing step：
(1) melt blending
It is 100 according to phthalonitrile and the mass ratio containing reactive hydrogen heterocyclic compound：(2~100) dispensing；
Under agitation phthalonitrile is heated to into molten condition, then heterocycle containing reactive hydrogen is added in the phthalonitrile of melting
Compound and mix homogeneously, stop heating and natural cooling after phthalonitrile and the mix homogeneously of heterocyclic compound containing reactive hydrogen
To room temperature, then phthalonitrile and blend containing reactive hydrogen heterocyclic compound are ground into into granule or powder, the neighbour
Benzene dicarbonitrile refers to the compound of phthalonitrile group, and general structure is as follows：
In formula, R1, R2, R3, R4For alkyl, phenyl, hydrogen atom or halogen atom；
(2) solidification of blend
By step (1) gained granule or powder blend under nitrogen atmosphere or oxygen atmosphere successively according to temperature below and guarantor
The warm time is solidified：0.0~5.0 hour is incubated at 280 DEG C of 220 DEG C≤T ＜；At 370 DEG C of 280 DEG C≤T ＜ insulation 0.5~
24.0 hours；0~24.0 hour is incubated at 370 DEG C≤T≤400 DEG C；Solidification cools to room temperature with the furnace and obtains final product adjacent benzene two after terminating
Formonitrile HCN resin.
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| CN101619131A (en) * | 2009-07-25 | 2010-01-06 | 大连理工大学 | O-phthalodinitrile end-blocked soluble polyarylether resin with phthalazinone structure and condensate and preparation method thereof |
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| CN101619131A (en) * | 2009-07-25 | 2010-01-06 | 大连理工大学 | O-phthalodinitrile end-blocked soluble polyarylether resin with phthalazinone structure and condensate and preparation method thereof |
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