CN105037721A - 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
- Publication number
- CN105037721A CN105037721A CN201510460529.6A CN201510460529A CN105037721A CN 105037721 A CN105037721 A CN 105037721A CN 201510460529 A CN201510460529 A CN 201510460529A CN 105037721 A CN105037721 A CN 105037721A
- Authority
- CN
- China
- Prior art keywords
- active hydrogen
- containing active
- phthalonitrile
- ring compound
- hydrogen
- 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.)
- Granted
Links
- 0 *C(CC(C1*)=O)NC1=O Chemical compound *C(CC(C1*)=O)NC1=O 0.000 description 2
- OUBLUKCIUHXYPI-PLNGDYQASA-N CC/C=C\C(C(NC(CC(N1)=O)NC1=O)=O)=C Chemical compound CC/C=C\C(C(NC(CC(N1)=O)NC1=O)=O)=C OUBLUKCIUHXYPI-PLNGDYQASA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N O=C(c(c1c2)ccc2Oc(cc2C(O3)=O)ccc2C3=O)OC1=O Chemical compound O=C(c(c1c2)ccc2Oc(cc2C(O3)=O)ccc2C3=O)OC1=O QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
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, particularly prepare the application in o-phthalonitrile resin containing active hydrogen heterogeneous ring compound.
Background technology
Heterogeneous ring compound (heterocycliccompound) refers to a compounds with ring texture.Form outside the atom carbon atom of ring, also at least containing a heteroatoms (non-carbon), heteroatoms comprises oxygen, sulphur, nitrogen etc.Heterogeneous ring compound is prevalent among the structure of drug molecule, and the important compound majority relevant with biology is heterogeneous ring compound, and such as nucleic acid, some VITAMIN, microbiotic, hormone, pigment and alkaloid etc., these heterogeneous ring compounds are multiplex makes medicine.Also synthesize varied heterogeneous ring compound with various performance at present, medicine, Insecticides (tech) & Herbicides (tech), dyestuff, plastics etc. can have been made.In addition, heterogeneous ring compound relies on excellent heat and thermo-oxidative stability, is usually used to prepare performance resins as raw material, as polyimide, and polybenzimidazole etc.It is heterogeneous ring compound finger ring at least with-NH-a structure containing active hydrogen heterogeneous ring compound.At present and have no document or research and propose and will be used as solidifying agent to accelerate o-phthalonitrile resin solidification containing active hydrogen heterogeneous ring compound.
Add the curing speed that solidifying agent can improve o-phthalonitrile resin to a certain extent, reduce its condition of cure simultaneously.Primary aromatic amine, organic acid, organic acid/ammonium salt and metal-salt, phenols or amine curing agent etc. all effectively can accelerate the solidification of o-phthalonitrile resin.But all there is a fatal shortcoming in above-mentioned solidifying agent: o-phthalonitrile resin usually needs the high temperature of long-time tolerance more than 300 DEG C when using as high temperature material, and amine and other solidifying agent thermostability at this high temperature and thermo-oxidative stability not good, this can reduce the use properties of resin.
Summary of the invention
The object of the present invention is to provide the novelty teabag containing active hydrogen heterogeneous ring compound, namely the application in o-phthalonitrile resin is being prepared, solidifying agent will be used as containing active hydrogen heterogeneous ring compound and accelerate o-phthalonitrile resin solidification, and improve thermostability and the thermo-oxidative stability of o-phthalonitrile resin.
The invention provides and confirm and can accelerate o-phthalonitrile resin solidification containing active hydrogen heterogeneous ring compound, can be used as the solidifying agent of o-phthalonitrile resin, apply preparing in o-phthalonitrile resin.
The above-mentioned active hydrogen heterogeneous ring compound that contains is preparing the application in o-phthalonitrile resin, described containing active hydrogen heterogeneous ring compound be containing active hydrogen carbazole, containing active hydrogen imidazoles, containing active hydrogen pyrimidine, containing active hydrogen purine, containing active hydrogen piperazine, containing active hydrogen pyrroles, containing active hydrogen pyrazoles, containing active hydrogen indazole, containing active hydrogen indoles, containing active hydrogen pyrrolopyridine, containing the one in active hydrogen phthalazone, their structural formula is as follows:
Containing active hydrogen carbazole:
Containing active hydrogen imidazoles:
Containing active hydrogen pyrimidine:
Containing active hydrogen purine:
Containing active hydrogen piperazine:
Containing active hydrogen pyrroles:
Containing active hydrogen pyrazoles:
Containing active hydrogen indazole:
Containing active hydrogen indoles:
Containing active hydrogen pyrrolopyridine:
Containing active hydrogen phthalazone:
In structure above, wavy line refers to and is connected with other atom, functional group or macromolecular main chain by covalent linkage herein.
The above-mentioned active hydrogen heterogeneous ring compound that contains is preparing the application in o-phthalonitrile resin, realizes by following processing step:
(1) melt blending
According to phthalonitrile be 100:(2 ~ 100 containing the mass ratio of active hydrogen heterogeneous ring compound) prepare burden;
Under agitation phthalonitrile is heated to molten state, add containing active hydrogen heterogeneous ring compound in the phthalonitrile of melting again and mix, when phthalonitrile with stop after mixing containing active hydrogen heterogeneous ring compound heat and naturally cooling to room temperature, then by phthalonitrile with contain the blend of active hydrogen heterogeneous ring compound and be ground into particle or Powdered;
(2) solidification of blend
Step (1) gained particle or Powdered blend are cured according to following temperature and soaking time successively under nitrogen atmosphere or oxygen atmosphere: at 220 DEG C≤T < 280 DEG C, be incubated 0.0 ~ 5.0 hour; 0.5 ~ 24.0 hour is incubated at 280 DEG C≤T < 370 DEG C; Insulation 0 ~ 24.0 hour at 370 DEG C≤T≤400 DEG C; Cool to room temperature with the furnace after solidification terminates and namely obtain o-phthalonitrile resin.
Phthalonitrile described in the present invention refers to the compound of phthalonitrile group, and general structure is as follows:
In formula, R
1, R
2, R
3, R
4can be alkyl, phenyl, hydrogen atom or halogen atom.
Compared with prior art, the present invention has following beneficial effect:
1, the present invention is that known compound contains active hydrogen heterogeneous ring compound and excavated new purposes, namely accelerates o-phthalonitrile resin solidification, can be used as the solidifying agent of o-phthalonitrile resin, has opened up containing the new Application Areas of active hydrogen heterogeneous ring compound.
2, the present invention will be used as solidifying agent containing active hydrogen heterogeneous ring compound, o-phthalonitrile resin is prepared with phthalonitrile is blended, utilize the solidification accelerating o-phthalonitrile resin containing active hydrogen heterogeneous ring compound, significantly improve solidification rate (see Fig. 2).Simultaneously owing to containing active hydrogen heterogeneous ring compound good heat stability, at high temperature not easily to volatilize decomposition, mechanical property and the thermal characteristics of the o-phthalonitrile resin can effectively avoiding o-phthalonitrile resin to cause because the thermotolerance of solidifying agent is lower in solidification and use procedure reduce, thus improve thermostability and the thermo-oxidative stability of o-phthalonitrile resin.From embodiment, the T5% of obtained o-phthalonitrile resin is all more than 480 DEG C, and carbon yield, also higher than 72%, and adds compared with arylamine class or phenols curing agent, and the thermostability of o-phthalonitrile resin and thermo-oxidative stability obtain raising to a certain extent.
3, utilization of the present invention accelerates o-phthalonitrile resin solidification containing active hydrogen heterogeneous ring compound, and equipment is conventional equipment, is thus convenient to suitability for industrialized production
Accompanying drawing explanation
Fig. 1 is the infrared spectrum in embodiment 1 before and after blend solidification.
Fig. 2 be in embodiment 1 blend and phthalonitrile monomer 1 at the flow curve figure of 325 DEG C of isothermal cures.
Fig. 3 is the TGA curve (at temperature rise rate 10 DEG C/min, recording under nitrogen atmosphere) in embodiment 1 before and after blend solidification.
Embodiment
Be described further preparing the application in o-phthalonitrile resin containing active hydrogen heterogeneous ring compound of the present invention below by embodiment.
Embodiment 1
The present embodiment is that active hydrogen purine formation accelerates o-phthalonitrile resin:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A1
VITAMIN B4 (Cas:73-24-5 is added in 100mL there-necked flask, 0.02mol, 2.70g), 60ml refines NMP, stirs after 10 minutes, adds pyromellitic dianhydride (PMDA wherein, 0.01mol, 2.18g), after stirring at room temperature 7h, in reaction system, add 20mL refined toluene, and system temperature is risen to 145 DEG C of backflow backflows, and react 7h at this temperature.Treat that no longer including water in system produces, raised temperature to 180 DEG C, separates the toluene in system, when question response system temperature sharply rises, illustrate that toluene removes substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and washes, the filter cake filtered, again filter cake is washed three times, methyl alcohol stirs washes twice, after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must be as follows containing active hydrogen heterogeneous ring compound A1. reaction formula:
(2) synthesis of phthalonitrile monomer 1
Reference literature TeddyM.Keller, DawnD.Dominguez, Hightemperatureresorcinol-basedphthalonitrilepolymer, polymer, 2005,46,4614-4618.
(3) melt blending
5.0g phthalonitrile monomer 1 is heated to molten state, in the phthalonitrile monomer of melting, 1.0g is added containing active hydrogen heterogeneous ring compound A6 according to phthalonitrile monomer and the mass ratio 100:20 containing active hydrogen heterogeneous ring compound A5, high speed machine stirs 4min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend;
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 275 DEG C, be incubated 2.0 hours; 2.0 hours are incubated at 325 DEG C; 2.0 hours are incubated at 375 DEG C; Room temperature is cooled to the furnace after solidification terminates.Infrared spectrum before and after blend solidification is shown in Fig. 1, and the flow curve figure of isothermal cure is shown in Fig. 2, and the TGA curve before and after blend solidification is shown in Fig. 3.
As seen from Figure 1, compared with the IR characteristic peak before solidifying with blend after blend solidification, main manifestations is: the IR characteristic peak 2234cm of O-phthalic itrile group
-1significantly weaken, illustrate that phthalonitrile groups reacts, blend has cured.
As can be seen from Figure 2, with the addition of on a small quantity containing active hydrogen heterogeneous ring compound monomer A 1, the solidification rate of phthalonitrile monomer 1 is obviously accelerated, and illustrates that can accelerate o-phthalonitrile resin containing active hydrogen heterogeneous ring compound solidifies.
As can be seen from Figure 3, blend solidifies, T after blend solidification
5%be 489.74 DEG C, carbon yield is 73.69%, illustrates that obtained o-phthalonitrile resin has excellent thermostability.
Embodiment 2
The present embodiment is that imidazoles accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A2
In 100mL there-necked flask, add (Cas:4919-03-30.02mol, 1.66g), 60ml refines NMP, stir after 10 minutes, add 3 wherein, 3,4,4-biphenyl dianhydride (BPDA, 0.01mol, 2.94g), after stirring at room temperature 7h, in reaction system, add 20mL refined toluene, and system temperature is risen to 145 DEG C of backflows, and react 5h at this temperature.Treat that no longer including water in system produces, raised temperature to 180 DEG C, separates the toluene in system, when question response system temperature sharply rises, illustrate that toluene removes substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and washes, the filter cake filtered, again filter cake is washed three times, methyl alcohol stirs washes twice, after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must contain active hydrogen heterogeneous ring compound A2.
(2) synthesis of phthalonitrile monomer 2
Synthesize according to method described in Publication about Document: D.Kumar, U.RazdanandA.D.Gupta, Thermallypolymerizablebisaryloxy-bisimido-bisphthalonitr ilescontainingdimethylsilane, hexafluoroisopropylidene, ether, andketogroups:Synthesis, characterization, andNMRstudy, 31,1993,2319-2331.
The structural formula of gained phthalonitrile monomer 2 is:
(3) melt blending
5.0g phthalonitrile monomer 2 is heated to molten state, in the phthalonitrile monomer of melting, 1.0g is added containing active hydrogen heterogeneous ring compound A2 according to phthalonitrile monomer and the mass ratio 100:20 containing active hydrogen heterogeneous ring compound A2, high speed machine stirs 2min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 260 DEG C, be incubated 4.0 hours; 12.0 hours are incubated at 330 DEG C; 2.0 hours are incubated at 390 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 494.37 DEG C, carbon yield is 72.63%.
Embodiment 3
The present embodiment is that pyrimidine can accelerate o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A3
In 500ml there-necked flask, add ODPA (0.10mol, 31.02g), 124mlNMP, oil bath is warming up to ODPA and can dissolves completely (temperature is about 70 DEG C, and now system is light yellow clear), then cools the temperature to room temperature.At room temperature in reaction solution, add cytosine(Cyt) (Cas:71-30-7,0.20mol, 22.22g), after stirring at room temperature 6h.Add 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 120 DEG C, and react 3h 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, methyl alcohol stirs washes twice, and after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must contain active hydrogen heterogeneous ring compound A3.
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2.
(3) melt blending
5.0g phthalonitrile monomer 2 is heated to molten state, in the phthalonitrile monomer of melting, 0.25g is added containing active hydrogen heterogeneous ring compound A3 according to phthalonitrile monomer and the mass ratio 100:5 containing active hydrogen heterogeneous ring compound A3, high speed machine stirs 2.5min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 260 DEG C, be incubated 4.0 hours; 10.0 hours are incubated at 350 DEG C; 3.0 hours are incubated at 380 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 505.33 DEG C, carbon yield is 78.19%.
Embodiment 4
The present embodiment is that pyrimidine accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A4
3 are added, 3,4 in 500ml there-necked flask, 4-biphenyl dianhydride (BPDA, 0.11mol, 32.36g), 132mlNMP, oil bath is warming up to BPDA and can dissolves completely (temperature is about 70 DEG C, and now system is light yellow clear), then cools the temperature to room temperature.At room temperature in reaction solution, add 6-amino uracil (0.22mol, 28.41g), after stirring at room temperature 5h.Add diacetyl oxide (0.66mol, 68.41g, 98.5%wt) and pyridine (0.66mol, 52.47g, 99.5%wt), and system temperature is risen to 130 DEG C, and react 4h 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, methyl alcohol stirs washes twice, and after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must contain active hydrogen heterogeneous ring compound A4.
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2
(3) melt blending
5.0g phthalonitrile monomer 2 is heated to molten state, in the phthalonitrile monomer of melting, 0.75g is added containing active hydrogen heterogeneous ring compound A4 according to phthalonitrile monomer and the mass ratio 100:15 containing active hydrogen heterogeneous ring compound A4, high speed machine stirs 3min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend;
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 260 DEG C, be incubated 4.0 hours; 12.0 hours are incubated at 340 DEG C; 4.0 hours are incubated at 375 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 495.33 DEG C, carbon yield is 72.57%.
Embodiment 5
The present embodiment is that carbazole accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A5
Synthesize according to method described in Publication about Document: YuChen, DandanHan, TaoWang, andXiuyanLi, EfficientSynthesisofArylatedCarbazolefromCyclopentadieny lironComplexes, Ind.Eng.Chem.Res.2013,52,3646-3652.
(2) synthesis of phthalonitrile monomer 2 is see embodiment 2
(3) melt blending
5.0g phthalonitrile monomer 2 is heated to molten state, in the phthalonitrile monomer of melting, 0.5g is added containing active hydrogen heterogeneous ring compound A1 according to phthalonitrile monomer and the mass ratio 100:10 containing active hydrogen heterogeneous ring compound A1, high speed machine stirs 3min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 270 DEG C, be incubated 3.0 hours; 20.0 hours are incubated at 340 DEG C; 4.0 hours are incubated at 390 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained phthalonitrile
5%be 500.37 DEG C, carbon yield is 76.73%.
Embodiment 6
The present embodiment is that isoquinoline 99.9 can accelerate o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A6
6-aminoisoquinoline-1 (2H)-one (Cas:216099-46-6 is added in 100mL there-necked flask, 0.02mol, 1.73g), 60ml refines NMP, stir after 10 minutes, add pyromellitic acid dianhydride (PMDA wherein, 0.01mol, 2.94g), after stirring at room temperature 5h, in reaction system, add 20mL refined toluene, and system temperature is risen to 145 DEG C of backflows, and react 7h at this temperature.Treat that no longer including water in system produces, raised temperature to 180 DEG C, separates the toluene in system, when question response system temperature sharply rises, illustrate that toluene removes substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and washes, the filter cake filtered, again filter cake is washed three times, methyl alcohol stirs washes twice, after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must contain active hydrogen heterogeneous ring compound A6.
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1.
(3) solution blending
5.0g phthalonitrile monomer 1 is added in 100mL tetrahydrofuran solution, after phthalonitrile monomer dissolves completely, 0.5g is added containing active hydrogen heterogeneous ring compound A6 in solution, after A6 dissolves, to pressurize 45 DEG C of dryings, dried powder is fully ground, namely obtains the blend of phthalonitrile and A7.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 240 DEG C, be incubated 3.0 hours; 18.0 hours are incubated at 340 DEG C; 5.0 hours are incubated at 390 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 500.37 DEG C, carbon yield is 76.72%.
Embodiment 7
The present embodiment is that purine accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A7
3 are added, 3,4 in 500ml there-necked flask, 4-biphenyl dianhydride (BPDA, 0.11mol, 32.36g), 132mlNMP, oil bath is warming up to PMDA and can dissolves completely (temperature is about 70 DEG C, and now system is light yellow clear), then cools the temperature to room temperature.At room temperature in reaction solution, add 6-amino-7-azapurine (Cas:1500-85-20.22mol, 29.51g), after stirring at room temperature 5h.Add diacetyl oxide (0.66mol, 68.41g, 98.5%wt) and pyridine (0.66mol, 52.47g, 99.5%wt), and system temperature is risen to 130 DEG C, and react 4h 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, methyl alcohol stirs washes twice, and after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must contain active hydrogen heterogeneous ring compound A7.
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2
(3) melt blending
5.0g phthalonitrile monomer 2 is heated to molten state, in the phthalonitrile monomer of melting, 0.75g is added containing active hydrogen heterogeneous ring compound A7 according to phthalonitrile monomer and the mass ratio 100:15 containing active hydrogen heterogeneous ring compound A7, high speed machine stirs 3min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend;
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 255 DEG C, be incubated 4.0 hours; 12.0 hours are incubated at 335 DEG C; 4.0 hours are incubated at 380 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 488.14 DEG C, carbon yield is 74.22%.
Embodiment 8
The present embodiment is that purine accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A8
3 are added, 3,4 in 500ml there-necked flask, 4-biphenyl dianhydride (BPDA, 0.11mol, 32.36g), 132mlNMP, oil bath is warming up to PMDA and can dissolves completely (temperature is about 70 DEG C, and now system is light yellow clear), then cools the temperature to room temperature.In reaction solution, at room temperature add 8-to mix nitrogen VITAMIN B4 (Cas:1123-54-20.22mol, 29.94g), after stirring at room temperature 5h.Add diacetyl oxide (0.66mol, 68.41g, 98.5%wt) and pyridine (0.66mol, 52.47g, 99.5%wt), and system temperature is risen to 130 DEG C, and react 4h 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, methyl alcohol stirs washes twice, and after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must contain active hydrogen heterogeneous ring compound A8.
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) melt blending
5.0g phthalonitrile monomer 1 is heated to molten state, in the phthalonitrile monomer of melting, 0.75g is added containing active hydrogen heterogeneous ring compound A8 according to phthalonitrile monomer and the mass ratio 100:15 containing active hydrogen heterogeneous ring compound A8, high speed machine stirs 3min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend;
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 255 DEG C, be incubated 4.0 hours; 12.0 hours are incubated at 335 DEG C; 4.0 hours are incubated at 380 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 497.14 DEG C, carbon yield is 74.22%.
Embodiment 9
The present embodiment is that piperazine accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A9
Synthesize according to method described in Publication about Document: MakiSeki, OsamuTsuruta, YukioAoyama, AkiSoejima, HiroshiShimada, andHikaruNonaka, SynthesisandPharmacologicalEvaluationof3-Amino-1-(5-indanyloxy)-2-propanolDerivativesasPotentSodiumChannelBlockersforthe TreatmentofStroke, Chem.Pharm.Bull., 2012,60 (4), 488 – 498.
Structural formula containing active hydrogen heterogeneous ring compound A9 is:
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1.
(3) melt blending
5.0g phthalonitrile monomer 1 is heated to molten state, in the phthalonitrile monomer of melting, 0.25g is added containing active hydrogen heterogeneous ring compound A9 according to phthalonitrile monomer and the mass ratio 100:5 containing active hydrogen heterogeneous ring compound A9, high speed machine stirs 1min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend;
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 260 DEG C, be incubated 4.0 hours; 12.0 hours are incubated at 330 DEG C; 2.0 hours are incubated at 390 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 486.01 DEG C, carbon yield is 76.19%.
Embodiment 10
The present embodiment is that isoquinolines accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A10
In 100mL there-necked flask, add 6-aminoisoquinoline ketone (Cas:22246-00-00.02mol, 3.24g), 60ml refines NMP, stir after 10 minutes, add 3 wherein, 3,4,4-biphenyl dianhydride (BPDA, 0.01mol, 2.94g), after stirring at room temperature 5h, in reaction system, add 20mL refined toluene, and system temperature is risen to 145 DEG C of backflows, and react 7h at this temperature.Treat that no longer including water in system produces, raised temperature to 180 DEG C, separates the toluene in system, when question response system temperature sharply rises, illustrate that toluene removes substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and washes, the filter cake filtered, again filter cake is washed three times, methyl alcohol stirs washes twice, after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must contain active hydrogen heterogeneous ring compound A10.Reaction formula is as follows:
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) solution blending
5.0g phthalonitrile monomer 1 is added in 100mL tetrahydrofuran solution, after phthalonitrile monomer dissolves completely, 0.6g is added containing active hydrogen heterogeneous ring compound A10 in solution, after A10 dissolves, to pressurize 45 DEG C of dryings, dried powder is fully ground, namely obtains the blend of phthalonitrile and A10.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 270 DEG C, be incubated 3.0 hours; 18.0 hours are incubated at 340 DEG C; 4.0 hours are incubated at 390 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 499.37 DEG C, carbon yield is 74.43%.
Embodiment 11
The present embodiment solidifies for pyrroles accelerates o-phthalonitrile resin:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A11
In 100mL there-necked flask, add 3-pyrroles's alkanamine (Cas:79286-79-60.02mol, 1.73g), 60ml refines NMP, stir after 10 minutes, add 3 wherein, 3,4,4-biphenyl dianhydride (BPDA, 0.01mol, 2.94g), after stirring at room temperature 5h, in reaction system, add 20mL refined toluene, and system temperature is risen to 145 DEG C of backflows, and react 5h at this temperature.Treat that no longer including water in system produces, raised temperature to 180 DEG C, separates the toluene in system, when question response system temperature sharply rises, illustrate that toluene removes substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and washes, the filter cake filtered, again filter cake is washed three times, methyl alcohol stirs washes twice, after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must be as follows containing active hydrogen heterogeneous ring compound A11. reaction formula:
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) solution blending
5.0g phthalonitrile monomer 1 is added in 100mL tetrahydrofuran solution, after phthalonitrile monomer dissolves completely, 0.5g is added containing active hydrogen heterogeneous ring compound A11 in solution, after A11 dissolves, to pressurize 45 DEG C of dryings, dried powder is fully ground, namely obtains the blend of phthalonitrile and A11.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 220 DEG C, be incubated 3.0 hours; 8.0 hours are incubated at 340 DEG C; 5.0 hours are incubated at 370 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 499.31 DEG C, carbon yield is 74.12%.
Embodiment 12
The present embodiment is that pyrrolidone accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A12
In 100mL there-necked flask, add 4-amino-2-Pyrrolidone (CAS:88016-17-5,0.02mol, 2.00g), 60ml refines NMP, stir after 10 minutes, add 3 wherein, 3,4,4-biphenyl dianhydride (BPDA, 0.01mol, 2.94g), after stirring at room temperature 7h, in reaction system, add 20mL refined toluene, and system temperature is risen to 145 DEG C of backflows, and react 5h at this temperature.Treat that no longer including water in system produces, raised temperature to 180 DEG C, separates the toluene in system, when question response system temperature sharply rises, illustrate that toluene removes substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and washes, the filter cake filtered, again filter cake is washed three times, methyl alcohol stirs washes twice, after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must be as follows containing active hydrogen heterogeneous ring compound A12. reaction formula:
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) solution blending
5.0g phthalonitrile monomer 1 is added in 100mL tetrahydrofuran solution, after phthalonitrile monomer dissolves completely, 0.3g is added containing active hydrogen heterogeneous ring compound A12 in solution, after A12 dissolves, to pressurize 45 DEG C of dryings, dried powder is fully ground, namely obtains the blend of phthalonitrile and A12.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 225 DEG C, be incubated 5.0 hours; 18.0 hours are incubated at 330 DEG C; 5.0 hours are incubated at 375 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 501.11 DEG C, carbon yield is 79.72%.
Embodiment 13
The present embodiment is that pyrazoles accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A13
Resorcinol (0.08mol is added in 250mL three-necked bottle, 8.08g) with salt of wormwood (0.252mol, 36g), then 160mLDMSO solution is added wherein, 10min is stirred under room temperature under nitrogen protective condition, then 4-nitropyrazole (Cas:2075-46-9 is added wherein, 0.17mol, 19.22g), after solution stirs 48h at 20 DEG C, cooling, reaction solution is poured in 500mL hot water to stir and wash, collected by suction filter cake, the large water gaging of filter cake rinses to neutral, filter cake a small amount of ethanol (50mL) is washed, collected by suction filter cake, under vacuum condition, 70 DEG C of dry 24h, namely obtain containing active hydrogen heterogeneous ring compound A13.Reaction formula is as follows:
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2.
(3) solution blending
5.0g phthalonitrile monomer 2 is added in 100mL tetrahydrofuran solution, after phthalonitrile monomer dissolves completely, 0.4g is added containing active hydrogen heterogeneous ring compound A13 in solution, after A13 dissolves, to pressurize 45 DEG C of dryings, dried powder is fully ground, namely obtains the blend of phthalonitrile and A13.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 230 DEG C, be incubated 5.0 hours; 17.0 hours are incubated at 340 DEG C; 5.0 hours are incubated at 375 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 498.08 DEG C, carbon yield is 79.32%.
Embodiment 14
The present embodiment is that indazole can accelerate o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A14
Resorcinol (0.08mol is added in 250mL three-necked bottle, 8.08g) with salt of wormwood (0.252mol, 36g), then 160mLDMSO solution is added wherein, 10min is stirred under room temperature under nitrogen protective condition, then 6-nitro indazole (Cas:7597-18-4 is added wherein, 0.17mol, 27.73g), after solution stirs 48h at 20 DEG C, cooling, reaction solution is poured in 500mL hot water to stir and wash, collected by suction filter cake, the large water gaging of filter cake rinses to neutral, filter cake a small amount of ethanol (100mL) is washed, collected by suction filter cake, under vacuum condition, 70 DEG C of dry 24h, namely obtain containing active hydrogen heterogeneous ring compound A14.Reaction formula is as follows:
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2.
(3) solution blending
5.0g phthalonitrile monomer 2 is added in 100mL tetrahydrofuran solution, after phthalonitrile monomer dissolves completely, 1.2g is added containing active hydrogen heterogeneous ring compound A14 in solution, after A14 dissolves, to pressurize 45 DEG C of dryings, dried powder is fully ground, namely obtains the blend of phthalonitrile and A14.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 230 DEG C, be incubated 5.0 hours; 24.0 hours are incubated at 340 DEG C; 6.0 hours are incubated at 380 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 488.18 DEG C, carbon yield is 72.51%.
Embodiment 15
The present embodiment is that indoline accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A15
Resorcinol (0.08mol is added in 250mL three-necked bottle, 8.08g) with salt of wormwood (0.252mol, 36g), then 160mLDMSO solution is added wherein, 10min is stirred under room temperature under nitrogen protective condition, then 6-nitroindoline quinoline (Cas:19727-83-4 is added wherein, 0.16mol, 26.26g), after solution stirs 48h at 20 DEG C, cooling, reaction solution is poured in 500mL hot water to stir and wash, collected by suction filter cake, the large water gaging of filter cake rinses to neutral, filter cake a small amount of ethanol (100mL) is washed, collected by suction filter cake, under vacuum condition, 70 DEG C of dry 24h, namely obtain containing active hydrogen heterogeneous ring compound A15.
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) melt blending
5.0g phthalonitrile monomer 1 is heated to molten state, in the phthalonitrile monomer of melting, 0.8g is added containing active hydrogen heterogeneous ring compound A15 according to phthalonitrile monomer and the mass ratio 100:16 containing active hydrogen heterogeneous ring compound A15, high speed machine stirs 2min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 260 DEG C, be incubated 1.0 hours; 14.0 hours are incubated at 330 DEG C; 5.0 hours are incubated at 380 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 497.17 DEG C, carbon yield is 73.71%.
Embodiment 16
The present embodiment is that indolone can accelerate o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A16
5-amino indole-2-ketone (Cas:20876-36-2 is added in 100mL there-necked flask, 0.02mol, 2.96g), 60ml refines NMP, stirs after 10 minutes, adds pyromellitic dianhydride (PMDA wherein, 0.01mol, 2.18g), after stirring at room temperature 7h, in reaction system, add 20mL refined toluene, and system temperature is risen to 145 DEG C of backflows, and react 7h at this temperature.Treat that no longer including water in system produces, raised temperature to 180 DEG C, separates the toluene in system, when question response system temperature sharply rises, illustrate that toluene removes substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and washes, the filter cake filtered, again filter cake is washed three times, methyl alcohol stirs washes twice, after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must be as follows containing active hydrogen heterogeneous ring compound A16. reaction formula:
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2.
(3) melt blending
5.0g phthalonitrile monomer 2 is heated to molten state, in the phthalonitrile monomer of melting, 0.7g is added containing active hydrogen heterogeneous ring compound A16 according to phthalonitrile monomer and the mass ratio 100:14 containing active hydrogen heterogeneous ring compound A16, high speed machine stirs 3min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 260 DEG C, be incubated 1.0 hours; 14.0 hours are incubated at 330 DEG C; 5.0 hours are incubated at 380 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 496.71 DEG C, carbon yield is 73.01%.
Embodiment 17
The present embodiment is that indoles accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A17
Resorcinol (0.08mol is added in 250mL three-necked bottle, 8.08g) with salt of wormwood (0.252mol, 36g), then 160mLDMSO solution is added wherein, 10min is stirred under room temperature under nitrogen protective condition, then 7-nitroindoline (Cas:6960-42-5 is added wherein, 0.17mol, 27.55g), after solution stirs 48h at 20 DEG C, cooling, reaction solution is poured in 500mL hot water to stir and wash, collected by suction filter cake, the large water gaging of filter cake rinses to neutral, filter cake a small amount of ethanol (100mL) is washed, collected by suction filter cake, under vacuum condition, 70 DEG C of dry 24h, namely obtain containing active hydrogen heterogeneous ring compound A17.Reaction formula is as follows:
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1.
(3) melt blending
5.0g phthalonitrile monomer 1 is heated to molten state, in the phthalonitrile monomer of melting, 0.5g is added containing active hydrogen heterogeneous ring compound A17 according to phthalonitrile monomer and the mass ratio 100:10 containing active hydrogen heterogeneous ring compound A17, high speed machine stirs 2min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 235 DEG C, be incubated 4.0 hours; 20.0 hours are incubated at 345 DEG C; 6.0 hours are incubated at 380 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 484.43 DEG C, carbon yield is 75.33%.
Embodiment 18
The present embodiment is that pyrrolopyridine accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A18
5-amino-1H-pyrrolo-[3 is added in 100mL there-necked flask, 2-B] pyridine (Cas:207849-66-9,0.02mol, 2.66g), 60ml refine NMP, stir after 10 minutes, add pyromellitic dianhydride (PMDA, 0.01mol, 2.18g) wherein, after stirring at room temperature 7h, in reaction system, add 20mL refined toluene, and system temperature is risen to 145 DEG C of backflows, and react 7h at this temperature.Treat that no longer including water in system produces, raised temperature to 180 DEG C, separates the toluene in system, when question response system temperature sharply rises, illustrate that toluene removes substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and washes, the filter cake filtered, again filter cake is washed three times, methyl alcohol stirs washes twice, after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must be as follows containing active hydrogen heterogeneous ring compound A18. reaction formula:
(2) embodiment 2 is shown in the synthesis of phthalonitrile monomer 2.
(3) melt blending
5.0g phthalonitrile monomer 2 is heated to molten state, in the phthalonitrile monomer of melting, 1.0g is added containing active hydrogen heterogeneous ring compound A18 according to phthalonitrile monomer and the mass ratio 100:20 containing active hydrogen heterogeneous ring compound A18, high speed machine stirs 3min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 250 DEG C, be incubated 5.0 hours; 16.0 hours are incubated at 340 DEG C; 2.0 hours are incubated at 380 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 488.26 DEG C, carbon yield is 70.78%.
Embodiment 19
The present embodiment is that pyrrolopyridine accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A19
7-amino-1H-pyrrolo-[2,3-C] pyridine [3,2-B] pyridine (Cas:165669-36-3 is added in 100mL there-necked flask, 0.02mol, 2.66g), 60ml refines NMP, stirs after 10 minutes, adds pyromellitic dianhydride (PMDA wherein, 0.01mol, 2.18g), after stirring at room temperature 7h, in reaction system, add 20mL refined toluene, and system temperature is risen to 145 DEG C of backflows, and react 7h at this temperature.Treat that no longer including water in system produces, raised temperature to 180 DEG C, separates the toluene in system, when question response system temperature sharply rises, illustrate that toluene removes substantially, close heating and stir, the system for the treatment of is down to room temperature, with hot water precipitation, stirs and washes, the filter cake filtered, again filter cake is washed three times, methyl alcohol stirs washes twice, after suction filtration, filter cake is 70 DEG C of dry 12h in vacuum drying oven, must be as follows containing active hydrogen heterogeneous ring compound A19. reaction formula:
(2) embodiment 1 is shown in the synthesis of phthalonitrile monomer 1
(3) melt blending
5.0g phthalonitrile monomer 1 is heated to molten state, in the phthalonitrile monomer of melting, 0.5g is added containing active hydrogen heterogeneous ring compound A19 according to phthalonitrile monomer and the mass ratio 100:10 containing active hydrogen heterogeneous ring compound A19, high speed machine stirs 2min, then stop heating, after naturally cooling to room temperature, gained solid mortar grinding powder is both obtained blend.
(4) solidification of blend
Step (3) gained blend is cured according to following temperature and soaking time under nitrogen atmosphere successively: at 250 DEG C, be incubated 4.0 hours; 19.0 hours are incubated at 340 DEG C; 3.0 hours are incubated at 380 DEG C; Room temperature is cooled to the furnace after solidification terminates.
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 493.16 DEG C, carbon yield is 77.04%.
Embodiment 20
The present embodiment is that phthalazone accelerates o-phthalonitrile resin solidification:
(1) containing the synthesis of active hydrogen heterogeneous ring compound A20
4-(4-hydroxy phenyl)-2 is added in 250mL three-necked bottle, 3-naphthyridine-1-ketone (0.09mol, 19.10g) with salt of wormwood (0.168mol, 24g), then 160mLDMSO solution is added wherein, 10min is stirred under room temperature under nitrogen protective condition, then 4-nitrophthalonitrile (0.08mol is added wherein, 13.85g), after solution stirs 48h at 20 DEG C, cooling, reaction solution is poured in 500mL hot water to stir and wash, collected by suction filter cake, the large water gaging of filter cake rinses to neutral, filter cake a small amount of ethanol (100mL) is washed, collected by suction filter cake, under vacuum condition, 70 DEG C of dry 24h, namely obtain containing active hydrogen heterogeneous ring compound A2, namely containing phthalazone phthalonitrile monomer.
Reaction formula is as follows:
(2) solidify containing phthalazone phthalonitrile monomer
Step (1) gained is cured according to following temperature and soaking time under nitrogen atmosphere successively containing phthalazone phthalonitrile monomer A20: at 230 DEG C, be incubated 12.0 hours; 12.0 hours are incubated at 340 DEG C; 5.0 hours are incubated at 375 DEG C;
In the present embodiment, in the infrared spectrum before and after blend solidification, the IR characteristic peak of O-phthalic itrile group is similar to Fig. 1, the T of gained o-phthalonitrile resin
5%be 498.08 DEG C, carbon yield is 73.72%.
Claims (2)
1. preparing the application in o-phthalonitrile resin containing active hydrogen heterogeneous ring compound.
2. preparing the application in o-phthalonitrile resin containing active hydrogen heterogeneous ring compound according to claim 1, it is characterized in that, described containing active hydrogen heterogeneous ring compound be containing active hydrogen carbazole, containing active hydrogen imidazoles, containing active hydrogen pyrimidine, containing active hydrogen purine, containing active hydrogen piperazine, containing active hydrogen pyrroles, containing active hydrogen pyrazoles, containing active hydrogen indazole, containing active hydrogen indoles, containing active hydrogen pyrrolopyridine, containing the one in active hydrogen phthalazone, their structural formula is as follows:
Containing active hydrogen carbazole:
Containing active hydrogen imidazoles:
Containing active hydrogen pyrimidine:
Containing active hydrogen purine:
Containing active hydrogen piperazine:
Containing active hydrogen pyrroles:
Containing active hydrogen pyrazoles:
Containing active hydrogen indazole:
Containing active hydrogen indoles:
Containing active hydrogen pyrrolopyridine:
Containing active hydrogen phthalazone:
In structure above, wavy line refers to and is connected with other atom, functional group or macromolecular main chain by covalent linkage herein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510460529.6A CN105037721B (en) | 2015-07-30 | 2015-07-30 | Application of active-hydrogen-containing heterocyclic compound to preparation of phthalonitrile resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510460529.6A CN105037721B (en) | 2015-07-30 | 2015-07-30 | Application of active-hydrogen-containing heterocyclic compound to preparation of phthalonitrile resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105037721A true CN105037721A (en) | 2015-11-11 |
| CN105037721B CN105037721B (en) | 2017-05-17 |
Family
ID=54444720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510460529.6A Active CN105037721B (en) | 2015-07-30 | 2015-07-30 | Application of active-hydrogen-containing heterocyclic compound to preparation of phthalonitrile resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105037721B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776636A (en) * | 2019-10-15 | 2020-02-11 | 四川大学 | Thermosetting resin based on imidazole dinitrile reactive groups and preparation method thereof |
| CN112812299A (en) * | 2020-12-31 | 2021-05-18 | 四川大学 | Phthalonitrile and amino acid cyclic peptide copolymer resin and preparation method thereof |
| US11730726B2 (en) | 2018-07-11 | 2023-08-22 | H. Lee Moffitt Cancer Center And Research Institute, Inc. | Dimeric immuno-modulatory compounds against cereblon-based mechanisms |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK151001B (en) * | 1976-08-18 | 1987-10-12 | Lilly Industries Ltd | PROCEDURE FOR TREATING FUNGUS INFECTION ON CULTURED PLANTS AND FUNGICID PREPARATION FOR USE IN PLANT PROTECTION |
| 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 |
| US20110108755A1 (en) * | 2009-11-12 | 2011-05-12 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Heteroaromatic phthalonitriles |
-
2015
- 2015-07-30 CN CN201510460529.6A patent/CN105037721B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK151001B (en) * | 1976-08-18 | 1987-10-12 | Lilly Industries Ltd | PROCEDURE FOR TREATING FUNGUS INFECTION ON CULTURED PLANTS AND FUNGICID PREPARATION FOR USE IN PLANT PROTECTION |
| 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 |
| US20110108755A1 (en) * | 2009-11-12 | 2011-05-12 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Heteroaromatic phthalonitriles |
Non-Patent Citations (2)
| Title |
|---|
| JIANGHUAI HU ET AL: "Study of the curing kinetics of a benzimidazole/phthalonitrile resin system", 《THERMOCHIMICA ACTA》 * |
| 赵永超 等: "含咪唑的自加速固化邻苯二甲腈化合物的性能研究", 《热固性树脂》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11730726B2 (en) | 2018-07-11 | 2023-08-22 | H. Lee Moffitt Cancer Center And Research Institute, Inc. | Dimeric immuno-modulatory compounds against cereblon-based mechanisms |
| CN110776636A (en) * | 2019-10-15 | 2020-02-11 | 四川大学 | Thermosetting resin based on imidazole dinitrile reactive groups and preparation method thereof |
| CN112812299A (en) * | 2020-12-31 | 2021-05-18 | 四川大学 | Phthalonitrile and amino acid cyclic peptide copolymer resin and preparation method thereof |
| CN112812299B (en) * | 2020-12-31 | 2022-03-29 | 四川大学 | Phthalonitrile and amino acid cyclic peptide copolymer resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105037721B (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101880389B (en) | Phthalonitrile-terminated polyimide resin containing phthalazinone structure, cured product and preparation method thereof | |
| CN105037721A (en) | Application of active-hydrogen-containing heterocyclic compound to preparation of phthalonitrile resin | |
| Wu et al. | Improving the curing process and thermal stability of phthalonitrile resin via novel mixed curing agents | |
| CN102504252B (en) | Amino phenoxy phthalonitrile pre-polymer, condensate and preparation method and application thereof | |
| CN101143928B (en) | Poly-o-phthalonitrile resin and its preparing process | |
| Amir et al. | Synthesis and characterization of self‐catalyzed imide‐containing pthalonitrile resins | |
| Agag et al. | Side‐chain type benzoxazine‐functional cellulose via click chemistry | |
| Selvakumar et al. | Synthesis, characterization and microwave-enhanced polymerization of a phthalonitrile resin | |
| Mallakpour et al. | Microwave‐assisted synthesis of new optically active poly (ester‐imide) s containing N, N′‐(pyromellitoyl)‐bis‐L‐phenylalanine moieties | |
| Mourad et al. | 4‐Hydroxy‐1‐phenylquinolin‐2 (1H)‐one in One‐pot Synthesis of Pyrimidoquinolines and Related Compounds under Microwave Irradiation and Conventional Conditions | |
| Avudaiappan et al. | Green synthesis of pyrazolopyranopyrimidinone and pyranopyrazole derivatives using porphyrin‐initiated amine‐functionalized PolyBCMO dendritic polymer as sonocatalyst | |
| CN104292230B (en) | Phthalimide-terminated monomer, preparation method and application thereof | |
| Faghihi et al. | Synthesis and properties of new poly (amide imide) s containing trimellitic rings and hydantoin moieties in the main chain under microwave irradiation | |
| US10844173B2 (en) | Method for the manufacture of a poly(imide) prepolymer powder and varnish, poly(imide) prepolymer powder and varnish prepared thereby, and poly(imide) prepared therefrom | |
| Mallakpour et al. | Synthesis of novel optically active poly (ester‐imide) s with benzophenone linkages by microwave‐assisted polycondensation | |
| Mallakpour et al. | Microwave‐assisted synthesis of optically active poly (amide imide) s derived from diacid chloride containing epiclon and l‐leucine with aromatic diamines | |
| CA2977536C (en) | Benzoxazine low temperature curable composition | |
| Zhou et al. | Synthesis, characterization and self-promoted cure behaviors of a new phthalonitrile derivative 4-(4-(3, 5-diaminobenzoyl) phenoxy) phthalonitrile | |
| CN101265322B (en) | Preparation method of cyano-containing benzoxazine resin | |
| CN101235131B (en) | Method for preparing benzoxazine intermediate containing propargyl ether and resin thereof | |
| R Jadhav et al. | New synthetic strategy for Friedlander condensation of 4‐amino‐2‐oxo‐2 H‐chromene‐3‐carbaldehyde by heterogeneous catalysis | |
| CN103408893B (en) | Maleimide phenolic resin/nano-TiO2 composite material and preparation method thereof | |
| CN106519296A (en) | Transparent halogen-free epoxy resin flame-resistant material and preparation method thereof | |
| Mallakpour et al. | Application of microwave irradiation for synthesis of novel optically active poly (amide imides) derived from diacid chloride containing epiclon and l‐isoleucine with aromatic diamines | |
| JP5618289B2 (en) | Gelling agent and gel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |