CN110256292A - The phthalonitrile monomer and the preparation method and application thereof with self-catalysis curing characteristics containing alkyl - Google Patents
The phthalonitrile monomer and the preparation method and application thereof with self-catalysis curing characteristics containing alkyl Download PDFInfo
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
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Abstract
The invention discloses a kind of phthalonitrile monomer and the preparation method and application thereof with self-catalysis curing characteristics containing alkyl, the phthalonitrile monomer containing alkyl, structural formula are as follows:
Description
Technical field
The invention belongs to technical field of polymer material processing, and being related to one kind containing alkyl has self-catalysis curing characteristics
Phthalonitrile compound and preparation method.
Background technique
O-phthalonitrile resin due to high thermal stability, thermo-oxidative stability, low combustible, chemical corrosion resistance with
And excellent mechanical behavior under high temperature, it is widely used in the high skill such as aerospace as the matrix resin of high-performance composite materials
Art field.O-phthalonitrile resin is to be formed by curing by phthalonitrile monomer, but existing phthalonitrile monomer is not reinforced
Agent carry out solidification be one extremely slow process (generally at 300 DEG C, one week or more time viscosity all cannot obviously on
Rise), lead to its processing difficulties, processing cost is high, to limit the application of the resinoid.Curing agent is added can be to a certain degree
The upper curing rate for improving o-phthalonitrile resin, while reducing its condition of cure.Primary aromatic amine, organic acid, organic acid/
Ammonium salt and metal salt, phenols or amine curing agent etc. can effectively accelerate the solidification of o-phthalonitrile resin, but there is solidification
Process small molecular curing agent inevitably volatilizees, to make material existing defects, service performance reduces (Sastri S
B, Keller T M.Phthalonitrile cure reaction with aromatic diamines[J].Journal
of Polymer Science Part A:Polymer Chemistry,1998,36(11):1885-1890.).By in neighbour
Phenolic hydroxyl group, primaquine, secondary amine isoreactivity group is introduced in benzene dicarbonitrile structure to form self-catalysis curing system and can effectively solve
State problem.But triazine ring is contained by the o-phthalonitrile resin product structure that phenolic hydroxyl group, primaquine, secondary amine catalysis obtain, is gathered
Isoindoline and phthalocyanine, structure is complicated is difficult to, and the conversion ratio of itrile group is low.On the other hand, self-catalysis phthalonitrile
The synthesis and purification of compound are often complex.(Hu J,Liu Y,Jiao Y,et al.Self-promoted
phthalimide-containing phthalonitrile resins with sluggish curing process and
Excellent thermal stability [J] .RSC Advances, 2015,5 (21): 16199-16206.) which increase
The preparation cost of o-phthalonitrile resin limits it and applies on a large scale.
In addition, the compound containing alkyl is prevalent in nature, such as lignin, while alkyl group is also being synthesized
It is widely present in resin, such as phenolic resin.But adjacent benzene two can be accelerated by having no document at present or researching and proposing alkyl group
The solidification of formonitrile HCN resin.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of phthalonitrile monomer containing alkyl with
Preparation method, and the phthalonitrile monomer containing alkyl are preparing the application in o-phthalonitrile resin.Described contains
The phthalonitrile monomer synthesis technology of alkyl is simple.It is used for preparing o-phthalonitrile resin, in the item that curing agent is not added
Solidification rate can be improved under part, and the resin obtained has excellent thermal stability and thermo-oxidative stability, product structure is main
It is not contain triazine ring based on isoindoline, structure is more controllable.
Phthalonitrile monomer of the present invention containing alkyl, structural formula are as follows:
In formula, R1For H, F, Cl, Br, I, CH3、CH2CH3、CH2CH2CH3、CH(CH3)2、CF3、OCH3、OCH2CH3、CH=CH2、C≡CH、C≡N、One of.R2、R3、R4、R5And R6It can be identical
It can also be different, be H, F, Cl, Br, I, CH3、CH2CH3、CF3、OCH3、NO2、C≡N、 OH、In
It is a kind of.
The step of preparation process of phthalonitrile monomer of the present invention containing alkyl is as follows:
Using two phenolic hydroxyl-compounds A, (3 or 4)-nitrophthalonitrile and catalyst B as raw material, two phenolic hydroxyl-compounds
The molar ratio of A and (3 or 4)-nitrophthalonitrile is 1.0:(2.0~3.3), two phenolic hydroxyl-compounds A and catalyst B's rubs
You are than being 1.0:(1.0~1.5)；
Wherein the structure of two phenolic hydroxyl-compounds A is as follows:
Two phenolic hydroxyl-compounds A, (3 or 4)-nitrophthalonitrile are dissolved in polar solvent jointly, added into solution
Enter catalyst B, 20~40 DEG C insulation reaction 10~15 hours.After reaction, reaction solution is used into deionized water and first respectively
Alcohol washs at least twice and collects filter cake, by filtration cakes torrefaction to constant weight up to the phthalonitrile monomer containing alkyl, structural formula
It is as follows:
In the step, the dosage of polar solvent is that the solid content in reaction solution is 10%~50%, the solid content=(two
The quality of phenolic hydroxyl-compounds A+(3 or 4)-nitrophthalonitrile quality): polar solvent volume, two phenolic hydroxyl-compounds A
The mass unit of (3 or 4)-nitrophthalonitrile is gram that the volume unit of polar solvent is milliliter；
In the structural formula of the two phenolic hydroxyl-compounds A and the phthalonitrile monomer containing alkyl, R1For H, F, Cl,
Br、I、CH3、CH2CH3、CH2CH2CH3、CH(CH3)2、C(CH3)3、CF3、OCH3、OCH2CH3、 CH=CH2、C
≡CH、C≡N、One of.R2、R3、R4、R5And R6Can be the same or different, be H, F, Cl,
Br、I、CH3、CH2CH3、C(CH3)3、CF3、OCH3、NO2、C≡N、 OH、One of.
The general formula of synthesis process are as follows:
In above-mentioned synthesis process, the catalyst B be sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, sodium hydroxide,
One of potassium hydroxide.The polar solvent be N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc),
One of hexamethylphosphoramide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP).
Phthalonitrile monomer of the present invention containing alkyl can be applied in preparing o-phthalonitrile resin.
The above-mentioned phthalonitrile monomer containing alkyl is preparing the application in o-phthalonitrile resin, is the neighbour that will contain alkyl
Benzene dicarbonitrile monomer is successively solidified according to following temperature and soaking time and (represents temperature in described below with T): 220≤T
0.0~5.0 hour is kept the temperature at 260 DEG C of <；0.0~5.0 hour is kept the temperature at 310 DEG C of 260≤T <；It is kept the temperature at 350 DEG C of 310≤T <
0.5~24.0 hour；0.0~10.0 hour is kept the temperature at 350≤T≤400 DEG C；Cooled to the furnace after solidification room temperature to get
To o-phthalonitrile resin.
Compared with prior art, the invention has the following advantages:
1, the present invention is that the compound containing alkyl has excavated new purposes, that is, accelerates the solidification of o-phthalonitrile resin,
New application field has been opened up for the compound containing alkyl.
2, due to introducing catalyst unit alkyl group in the phthalonitrile monomer of the present invention for having alkyl, thus can
Realize self-catalysis solidification, compared with existing phthalonitrile monomer, the solidification rate in the application for preparing o-phthalonitrile resin
It significantly improves, the thermal stability and thermo-oxidative stability of obtained o-phthalonitrile resin are excellent.
3, the cured product of the phthalonitrile monomer of the present invention containing alkyl is different from amino, phenolic hydroxyl group catalysis,
The structure of cured product is mainly based on poly- isoindoline, no triazine ring.
Detailed description of the invention
Fig. 1 solidifies the infrared spectrogram of front and back for bisphenol-f type phthalonitrile obtained in embodiment 1.
Isothermal rheogram of the Fig. 2 for bisphenol-f type phthalonitrile obtained in embodiment 1 at 310 DEG C.
Fig. 3 solidifies the thermogravimetric curve of front and back for bisphenol-f type phthalonitrile obtained in embodiment 1.(in heating rate 10
DEG C/min, measured under nitrogen atmosphere).
Specific embodiment
Below by specific embodiment to the O-phthalic with self-catalysis curing characteristics of the present invention containing alkyl
Nitrile monomer and preparation method thereof is described further.
In following embodiment, (1)1HNMR test, i.e. nuclear magnetic resonance spectroscopy (1H NMR) it is by German Bruker Avance-
400NMR instrument test obtains, and solvent is DMSO-d6 or CDCl3；(2) infrared spectroscopy (FTIR) uses potassium bromide (KBr) tabletting
Method is tested on U.S.'s Nicolet FTIR-460 type Fourier transformation infrared spectrometer.；(3) rheometer test data are logical
Crossing storage modulus is to test to obtain by plate (diameter 25mm) rotational rheometer；(4) TGA, T5%: refer to sample in thermogravimetric
In analyzer TG, under the Elevated Temperature Conditions of 10 DEG C/min, nitrogen atmosphere, the temperature of weightlessness 5%；(5) carbon yield refers to that sample exists
Residual weight in thermogravimetric analyzer TG, under the Elevated Temperature Conditions of 10 DEG C/min, nitrogen atmosphere, when reaching 800 DEG C.
Embodiment 1
(1) preparation of monomer
Using 3.01g Bisphenol F (No. CAS: 620-92-8), 4- nitrophthalonitrile and potassium carbonate as raw material, Bisphenol F with
The molar ratio of 4- nitrophthalonitrile is 1.0:2.3, and the molar ratio of Bisphenol F and potassium carbonate is 1.0:1.1；
Wherein the structure of Bisphenol F is as follows:
Bisphenol F, 4- nitrophthalonitrile are dissolved in jointly in the nmp solvent of 20mL, carbonic acid is then added into solution
Potassium, 30 DEG C insulation reaction 12 hours.After reaction, reaction solution is washed twice and is collected with deionized water and methanol respectively
Filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from Bisphenol F,1H-NMR structural formula is as follows:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 250 DEG C keep the temperature 5.0 hours；280 DEG C keep the temperature 3.5 hours；310 DEG C of guarantors
Temperature 12.0 hours；370 DEG C keep the temperature 3.0 hours, cool to room temperature after solidification with the furnace to get o-phthalonitrile resin is arrived.Gu
Change product compared with the IR characteristic peak of raw material, is mainly shown as: the IR characteristic peak 2229cm of itrile group in o-phthalonitrile resin-1
It is apparent to weaken, almost disappear.Isoindoline 1660cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520
Or 1360cm-1Characteristic peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is equal
It is significantly less than 1.00Pa (0.00-1.00Pa), the storage modulus after solidification is above 0.1MPa.TGA:T5%: 486.6 DEG C；It is residual
Charcoal rate: 72.1%.In terms of comprehensive, a kind of adjacent benzene two for capableing of self-catalysis solidification and machinability and Good Heat-resistance is obtained
Formonitrile HCN resin.
Rheometer test: initial storage modulus: 0.07Pa be fully cured after storage modulus: 0.15MPa
TGA:T5%:486.6 DEG C of carbon yield: 72.1%
Embodiment 2
(1) preparation of monomer
Using 3.2g dihydric phenol (No. CAS: 2081-08-5), 4- nitrophthalonitrile and potassium carbonate as raw material, dihydric phenol with
The molar ratio of 4- nitrophthalonitrile is 1.0:2.3, and the molar ratio of dihydric phenol and potassium carbonate is 1.0:1.1；
Wherein the structure of dihydric phenol is as follows:
Dihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the nmp solvent of 25mL, carbonic acid is then added into solution
Potassium, 30 DEG C insulation reaction 10 hours.After reaction, reaction solution is washed twice and is collected with deionized water and methanol respectively
Filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding dihydric phenol,1H-NMR structural formula is as follows:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 230 DEG C keep the temperature 4.5 hours；270 DEG C keep the temperature 3.0 hours；320 DEG C of guarantors
Temperature 8.5 hours；375 DEG C keep the temperature 3.0 hours, cool to room temperature after solidification with the furnace to get o-phthalonitrile resin is arrived.Solidification
Product is mainly shown as compared with the IR characteristic peak of raw material: the IR characteristic peak 2229cm of itrile group in o-phthalonitrile resin-1It is bright
Aobvious decrease, almost disappears.Isoindoline 1660 and 1090cm can be observed simultaneously-1Characteristic peak, but without triazine ring
1520 or 1360cm-1Characteristic peak.The isothermal rheology test curve of curing system shows the energy storage mould of curing system before curing
Amount is significantly less than 1.00Pa (0.00-1.00Pa), and the storage modulus after solidification is above 0.1MPa.TGA:T5%: 470.6
℃；Carbon yield: 71.5%.In terms of comprehensive, a kind of self-catalysis solidification and machinability and Good Heat-resistance of capableing of is obtained
O-phthalonitrile resin.
Rheometer test: initial storage modulus: 0.06Pa be fully cured after storage modulus: 0.21MPa
TGA:T5%:470.6 DEG C of carbon yield: 71.5%
Embodiment 3
(1) preparation of monomer
Using 3.3g dihydric phenol (No. CAS: 1576-13-2), 4- nitrophthalonitrile and potassium carbonate as raw material, dihydric phenol with
The molar ratio of 4- nitrophthalonitrile is 1.0:2.3, and the molar ratio of dihydric phenol and potassium carbonate is 1.0:1.1；
Wherein the structure of dihydric phenol is as follows:
Dihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the DMSO solvent of 26mL, carbon is then added into solution
Sour potassium, 25 DEG C insulation reaction 15 hours.After reaction, reaction solution is washed twice and is received with deionized water and methanol respectively
Collect filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding dihydric phenol,1H-NMR structural formula is such as
Under:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 240 DEG C keep the temperature 3.0 hours；265 DEG C keep the temperature 4.5 hours；330 DEG C of guarantors
Temperature 11.0 hours；360 DEG C keep the temperature 3.5 hours, cool to room temperature after solidification with the furnace to get o-phthalonitrile resin is arrived.Gu
Change product compared with the IR characteristic peak of raw material, is mainly shown as: the IR characteristic peak 2229cm of itrile group in o-phthalonitrile resin-1
It is apparent to weaken, almost disappear.Isoindoline 1090cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520
Or 1360cm-1Characteristic peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is equal
It is significantly less than 1.00Pa (0.00-1.00Pa), the storage modulus after solidification is above 0.1MPa.TGA:T5%: 459.5 DEG C；It is residual
Charcoal rate: 71.2%.In terms of comprehensive, a kind of adjacent benzene two for capableing of self-catalysis solidification and machinability and Good Heat-resistance is obtained
Formonitrile HCN resin.
Rheometer test: initial storage modulus: 0.05Pa be fully cured after storage modulus: 0.23MPa
TGA:T5%:459.5 DEG C of carbon yield: 71.2%
Embodiment 4
(1) preparation of monomer
Using 4.5g dihydric phenol (No. CAS: 17619-01-1), 4- nitrophthalonitrile and sodium carbonate as raw material, dihydric phenol
It is 1.0:2.3 with the molar ratio of 4- nitrophthalonitrile, the molar ratio of dihydric phenol and sodium carbonate is 1.0:1.1；
Wherein the structure of dihydric phenol is as follows:
Dihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the DMSO solvent of 30mL, carbon is then added into solution
Sour sodium, 35 DEG C insulation reaction 13 hours.After reaction, reaction solution is washed twice and is received with deionized water and methanol respectively
Collect filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding dihydric phenol,1H-NMR structural formula is such as
Under:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 255 DEG C keep the temperature 3.5 hours；280 DEG C keep the temperature 3.0 hours；320 DEG C of guarantors
Temperature 15.0 hours；370 DEG C keep the temperature 4.5 hours, cool to room temperature after solidification with the furnace to get o-phthalonitrile resin is arrived.Gu
Change product compared with the IR characteristic peak of raw material, is mainly shown as: the IR characteristic peak 2231cm of itrile group in o-phthalonitrile resin-1
It is apparent to weaken, almost disappear.Isoindoline 1092cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520
Or 1360cm-1Characteristic peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is equal
It is significantly less than 1.00Pa (0.00-1.00Pa), the storage modulus after solidification is above 0.1MPa.TGA:T5%: 475.2 DEG C；It is residual
Charcoal rate: 71.6%.In terms of comprehensive, a kind of adjacent benzene two for capableing of self-catalysis solidification and machinability and Good Heat-resistance is obtained
Formonitrile HCN resin.
Rheometer test: initial storage modulus: 0.08Pa be fully cured after storage modulus: 0.31MPa
TGA:T5%:475.2 DEG C of carbon yield: 71.6%
Embodiment 5
(1) preparation of monomer
Using 4.8g dihydric phenol (No. CAS: 17619-01-1), 4- nitrophthalonitrile and potassium carbonate as raw material, dihydric phenol
It is 1.0:2.3 with the molar ratio of 4- nitrophthalonitrile, the molar ratio of dihydric phenol and potassium carbonate is 1.0:1.1；
Wherein the structure of dihydric phenol is as follows:
Dihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the DMSO solvent of 35mL, carbon is then added into solution
Sour potassium, 25 DEG C insulation reaction 11 hours.After reaction, reaction solution is washed twice and is received with deionized water and methanol respectively
Collect filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding dihydric phenol,1H-NMR structural formula is such as
Under:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 235 DEG C keep the temperature 5.0 hours；290 DEG C keep the temperature 4.0 hours；335 DEG C of guarantors
Temperature 14.5 hours；380 DEG C keep the temperature 3.5 hours, cool to room temperature after solidification with the furnace to get o-phthalonitrile resin is arrived.Gu
Change product compared with the IR characteristic peak of raw material, is mainly shown as: the IR characteristic peak 2231cm of itrile group in o-phthalonitrile resin-1
It is apparent to weaken, almost disappear.Isoindoline 1089cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520
Or 1360cm-1Characteristic peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is equal
It is significantly less than 1.00Pa (0.00-1.00Pa), the storage modulus after solidification is above 0.1MPa.TGA:T5%: 462.3 DEG C；It is residual
Charcoal rate: 70.6%.In terms of comprehensive, a kind of adjacent benzene two for capableing of self-catalysis solidification and machinability and Good Heat-resistance is obtained
Formonitrile HCN resin.
Rheometer test: initial storage modulus: 0.1Pa be fully cured after storage modulus: 0.18MPa
TGA:T5%:462.3 DEG C of carbon yield: 70.6%
Embodiment 6
(1) preparation of monomer
Using 5.0g dihydric phenol (No. CAS: 103330-88-7), 4- nitrophthalonitrile and potassium carbonate as raw material, dihydric phenol
It is 1.0:2.3 with the molar ratio of 4- nitrophthalonitrile, the molar ratio of dihydric phenol and potassium carbonate is 1.0:1.1；
Wherein the structure of dihydric phenol is as follows:
Dihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the DMSO solvent of 45mL, carbon is then added into solution
Sour potassium, 28 DEG C insulation reaction 11 hours.After reaction, reaction solution is washed twice and is received with deionized water and methanol respectively
Collect filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding dihydric phenol,1H-NMR structural formula is such as
Under:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 250 DEG C keep the temperature 2.0 hours；280 DEG C keep the temperature 3.5 hours；315 DEG C of guarantors
Temperature 17.0 hours；385 DEG C keep the temperature 2.0 hours, cool to room temperature after solidification with the furnace to get o-phthalonitrile resin is arrived.Gu
Change product compared with the IR characteristic peak of raw material, is mainly shown as: the IR characteristic peak 2231cm of itrile group in o-phthalonitrile resin-1
It is apparent to weaken, almost disappear.Isoindoline 1090cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520
Or 1360cm-1Characteristic peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is equal
It is significantly less than 1.00Pa (0.00-1.00Pa), the storage modulus after solidification is above 0.1MPa.TGA:T5%: 457.3 DEG C；It is residual
Charcoal rate: 70.8%.In terms of comprehensive, a kind of adjacent benzene two for capableing of self-catalysis solidification and machinability and Good Heat-resistance is obtained
Formonitrile HCN resin.
Rheometer test: initial storage modulus: 0.07Pa be fully cured after storage modulus: 0.18MPa
TGA:T5%:457.3 DEG C of carbon yield: 70.8%
Embodiment 7
(1) preparation of monomer
Using 4.0g dihydric phenol (No. CAS: 93006-77-0), 4- nitrophthalonitrile and potassium carbonate as raw material, dihydric phenol
It is 1.0:2.3 with the molar ratio of 4- nitrophthalonitrile, the molar ratio of dihydric phenol and potassium carbonate is 1.0:1.1；
Wherein the structure of dihydric phenol is as follows:
Dihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the DMSO solvent of 35mL, carbon is then added into solution
Sour potassium, 32 DEG C insulation reaction 13 hours.After reaction, reaction solution is washed twice and is received with deionized water and methanol respectively
Collect filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding dihydric phenol,1H-NMR structural formula is such as
Under:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 260 DEG C keep the temperature 4.0 hours；285 DEG C keep the temperature 5.0 hours；340 DEG C of guarantors
Temperature 11.5 hours；385 DEG C keep the temperature 6.0 hours, cool to room temperature after solidification with the furnace to get o-phthalonitrile resin is arrived.Gu
Change product compared with the IR characteristic peak of raw material, is mainly shown as: the IR characteristic peak 2230cm of itrile group in o-phthalonitrile resin-1It is bright
Aobvious decrease, almost disappears.Isoindoline 1090cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520 or
1360cm-1Characteristic peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is bright
Aobvious to be less than 1.00Pa (0.00-1.00Pa), the storage modulus after solidification is above 0.1MPa.TGA:T5%: 467.4 DEG C；Carbon residue
Rate: 71.5%.In terms of comprehensive, a kind of O-phthalic for capableing of self-catalysis solidification and machinability and Good Heat-resistance is obtained
Nitrile resin.
Rheometer test: initial storage modulus: 0.11Pa be fully cured after storage modulus: 0.24MPa
TGA:T5%:467.4 DEG C of carbon yield: 71.5%
Embodiment 8
(1) preparation of monomer
Using 4.8g dihydric phenol (No. CAS: 10218-59-4), 4- nitrophthalonitrile and potassium carbonate as raw material, dihydric phenol
It is 1.0:2.3 with the molar ratio of 4- nitrophthalonitrile, the molar ratio of dihydric phenol and potassium carbonate is 1.0:1.1；
Wherein the structure of dihydric phenol is as follows:
Dihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the DMSO solvent of 35mL, carbon is then added into solution
Sour potassium, 20 DEG C insulation reaction 13 hours.After reaction, reaction solution is washed twice and is received with deionized water and methanol respectively
Collect filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding dihydric phenol,1H-NMR structural formula is such as
Under:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 240 DEG C keep the temperature 5.0 hours；280 DEG C keep the temperature 3.0 hours；310 DEG C of guarantors
Temperature 16.0 hours；350 DEG C keep the temperature 3.5 hours, cool to room temperature after solidification with the furnace to get o-phthalonitrile resin is arrived.Gu
Change product compared with the IR characteristic peak of raw material, is mainly shown as: the IR characteristic peak 2229cm of itrile group in o-phthalonitrile resin-1
It is apparent to weaken, almost disappear.Isoindoline 1090cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520
Or 1360cm-1Characteristic peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is equal
It is significantly less than 1.00Pa (0.00-1.00Pa), the storage modulus after solidification is above 0.1MPa.TGA:T5%: 451.2 DEG C；It is residual
Charcoal rate: 70.2%.In terms of comprehensive, a kind of adjacent benzene two for capableing of self-catalysis solidification and machinability and Good Heat-resistance is obtained
Formonitrile HCN resin.
Rheometer test: initial storage modulus: 0.12Pa be fully cured after storage modulus: 0.18MPa
TGA:T5%:451.2 DEG C of carbon yield: 70.2%
Embodiment 9
(1) preparation of monomer
Using 5.8g dihydric phenol (No. CAS: 13004-51-8), 4- nitrophthalonitrile and potassium carbonate as raw material, dihydric phenol
It is 1.0:2.3 with the molar ratio of 4- nitrophthalonitrile, the molar ratio of dihydric phenol and potassium carbonate is 1.0:1.1；
Wherein the structure of dihydric phenol is as follows:
Dihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the DMAc solvent of 45mL, carbon is then added into solution
Sour potassium, 40 DEG C insulation reaction 13 hours.After reaction, reaction solution is washed twice and is received with deionized water and methanol respectively
Collect filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding dihydric phenol,1H-NMR structural formula is such as
Under:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 280 DEG C keep the temperature 5.0 hours；310 DEG C keep the temperature 15.0 hours；375℃
Heat preservation 6.0 hours cools to room temperature with the furnace to get o-phthalonitrile resin is arrived after solidification.The IR of cured product and raw material
Characteristic peak is compared, and is mainly shown as: the IR characteristic peak 2230cm of itrile group in o-phthalonitrile resin-1It is apparent to weaken, it is almost complete
It totally disappeared mistake.Isoindoline 1091cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520 or 1360cm-1Feature
Peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is significantly less than 1.00Pa
(0.00-1.00Pa), the storage modulus after solidification are above 0.1MPa.TGA:T5%: 494.2 DEG C；Carbon yield: 73.1%.It is comprehensive
For, obtain a kind of o-phthalonitrile resin for capableing of self-catalysis solidification and machinability and Good Heat-resistance.
Rheometer test: initial storage modulus: 0.06Pa be fully cured after storage modulus: 0.31MPa
TGA:T5%:494.2 DEG C of carbon yield: 73.1%
Embodiment 10
(1) preparation of monomer
Using 3.5g dihydric phenol (No. CAS: 93717-58-9), 4- nitrophthalonitrile and potassium carbonate as raw material, dihydric phenol
It is 1.0:2.3 with the molar ratio of 4- nitrophthalonitrile, the molar ratio of dihydric phenol and potassium carbonate is 1.0:1.1；
Wherein the structure of dihydric phenol is as follows:
Dihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the DMSO solvent of 32mL, carbon is then added into solution
Sour potassium, 40 DEG C insulation reaction 15 hours.After reaction, reaction solution is washed twice and is received with deionized water and methanol respectively
Collect filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding dihydric phenol,1H-NMR structural formula is such as
Under:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 240 DEG C keep the temperature 5.0 hours；280 DEG C keep the temperature 3.5 hours；310 DEG C of guarantors
Temperature 13.5 hours；390 DEG C keep the temperature 3.0 hours, cool to room temperature after solidification with the furnace to get o-phthalonitrile resin is arrived.Gu
Change product compared with the IR characteristic peak of raw material, is mainly shown as: the IR characteristic peak 2232cm of itrile group in o-phthalonitrile resin-1
It is apparent to weaken, almost disappear.Isoindoline 1091cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520
Or 1360cm-1Characteristic peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is equal
It is significantly less than 1.00Pa (0.00-1.00Pa), the storage modulus after solidification is above 0.1MPa.TGA:T5%: 507.3 DEG C；It is residual
Charcoal rate: 73.5%.In terms of comprehensive, a kind of adjacent benzene two for capableing of self-catalysis solidification and machinability and Good Heat-resistance is obtained
Formonitrile HCN resin.
Rheometer test: initial storage modulus: 0.09Pa be fully cured after storage modulus: 0.42MPa
TGA:T5%:507.3 DEG C of carbon yield: 73.5%
Embodiment 11
(1) preparation of monomer
Using 4.8g dihydric phenol (No. CAS: 4081-02-1), 4- nitrophthalonitrile and potassium carbonate as raw material, dihydric phenol with
The molar ratio of 4- nitrophthalonitrile is 1.0:2.3, and the molar ratio of dihydric phenol and potassium carbonate is 1.0:1.1；
Wherein the structure of dihydric phenol is as follows:
Dihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the DMSO solvent of 40mL, carbon is then added into solution
Sour potassium, 35 DEG C insulation reaction 10 hours.After reaction, reaction solution is washed twice and is received with deionized water and methanol respectively
Collect filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding dihydric phenol,1H-NMR structural formula is such as
Under:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 280 DEG C keep the temperature 4.0 hours；330 DEG C keep the temperature 14.0 hours；380℃
Heat preservation 6.0 hours cools to room temperature with the furnace to get o-phthalonitrile resin is arrived after solidification.The IR of cured product and raw material
Characteristic peak is compared, and is mainly shown as: the IR characteristic peak 2230cm of itrile group in o-phthalonitrile resin-1It is apparent to weaken, it is almost complete
It totally disappeared mistake.Isoindoline 1090cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520 or 1360cm-1Feature
Peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is significantly less than 1.00Pa
(0.00-1.00Pa), the storage modulus after solidification are above 0.1MPa.TGA:T5%: 496.2 DEG C；Carbon yield: 71.8%.It is comprehensive
For, obtain a kind of o-phthalonitrile resin for capableing of self-catalysis solidification and machinability and Good Heat-resistance.
Rheometer test: initial storage modulus: 0.09Pa be fully cured after storage modulus: 0.22MPa
TGA:T5%:496.2 DEG C of carbon yield: 71.8%
Embodiment 12
(1) preparation of monomer
Using 5.6g dihydric phenol (No. CAS: 109690-03-1), 4- nitrophthalonitrile and potassium carbonate as raw material, dihydric phenol
It is 1.0:2.3 with the molar ratio of 4- nitrophthalonitrile, the molar ratio of dihydric phenol and potassium carbonate is 1.0:1.1；
Wherein the structure of dihydric phenol is as follows:
Dihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the DMSO solvent of 45mL, carbon is then added into solution
Sour sodium, 35 DEG C insulation reaction 15 hours.After reaction, reaction solution is washed twice and is received with deionized water and methanol respectively
Collect filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding dihydric phenol,1H-NMR structural formula is such as
Under:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 280 DEG C keep the temperature 4.5 hours；340 DEG C keep the temperature 14.5 hours；385℃
Heat preservation 5.0 hours cools to room temperature with the furnace to get o-phthalonitrile resin is arrived after solidification.The IR of cured product and raw material
Characteristic peak is compared, and is mainly shown as: the IR characteristic peak 2231cm of itrile group in o-phthalonitrile resin-1It is apparent to weaken, it is almost complete
It totally disappeared mistake.Isoindoline 1089cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520 or 1360cm-1Feature
Peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is significantly less than 1.00Pa
(0.00-1.00Pa), the storage modulus after solidification are above 0.1MPa.TGA:T5%: 502.4 DEG C；Carbon yield: 72.3%.It is comprehensive
For, obtain a kind of o-phthalonitrile resin for capableing of self-catalysis solidification and machinability and Good Heat-resistance.
Rheometer test: initial storage modulus: 0.13Pa be fully cured after storage modulus: 0.23MPa
TGA:T5%:502.4 DEG C of carbon yield: 72.3%
Embodiment 13
(1) preparation of monomer
Using 5.8g trihydric phenol (No. CAS: 603-44-1), 4- nitrophthalonitrile and sodium carbonate as raw material, trihydric phenol with
The molar ratio of 4- nitrophthalonitrile is 1.0:3.3, and the molar ratio of trihydric phenol and sodium carbonate is 1.0:1.1；
Wherein the structure of trihydric phenol is as follows:
Trihydric phenol, 4- nitrophthalonitrile are dissolved in jointly in the DMSO solvent of 45mL, carbon is then added into solution
Sour sodium, 40 DEG C insulation reaction 13 hours.After reaction, reaction solution is washed twice and is received with deionized water and methanol respectively
Collect filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from corresponding trihydric phenol,1H-NMR structural formula is such as
Under:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 250 DEG C keep the temperature 5.0 hours；280 DEG C keep the temperature 6.0 hours；310 DEG C of guarantors
Temperature 12.0 hours；370 DEG C keep the temperature 5.0 hours, cool to room temperature after solidification with the furnace to get o-phthalonitrile resin is arrived.Gu
Change product compared with the IR characteristic peak of raw material, is mainly shown as: the IR characteristic peak 2230cm of itrile group in o-phthalonitrile resin-1
It is apparent to weaken, almost disappear.Isoindoline 1090cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520
Or 1360cm-1Characteristic peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is equal
It is significantly less than 1.00Pa (0.00-1.00Pa), the storage modulus after solidification is above 0.1MPa.TGA:T5%: 517.5 DEG C；It is residual
Charcoal rate: 74.2%.In terms of comprehensive, a kind of adjacent benzene two for capableing of self-catalysis solidification and machinability and Good Heat-resistance is obtained
Formonitrile HCN resin.
Rheometer test: initial storage modulus: 0.08Pa be fully cured after storage modulus: 0.47MPa
TGA:T5%:517.5 DEG C of carbon yield: 74.2%
Embodiment 14
(1) preparation of monomer
Using 3.32g Bisphenol F (No. CAS: 620-92-8), 3- nitrophthalonitrile and potassium carbonate as raw material, Bisphenol F with
The molar ratio of 3- nitrophthalonitrile is 1.0:2.2, and the molar ratio of Bisphenol F and potassium carbonate is 1.0:1.2；
Wherein the structure of Bisphenol F is as follows:
Bisphenol F, 3- nitrophthalonitrile are dissolved in jointly in the nmp solvent of 20mL, carbonic acid is then added into solution
Potassium, 32 DEG C insulation reaction 10 hours.After reaction, reaction solution is washed twice and is collected with deionized water and methanol respectively
Filter cake, by filtration cakes torrefaction to constant weight up to phthalonitrile monomer derived from Bisphenol F,1H-NMR structural formula is as follows:
(2) preparation of o-phthalonitrile resin
By the phthalonitrile monomer with self-catalysis curing characteristics containing alkyl made from step (1) successively according to following
Temperature and soaking time, are solidified under nitrogen atmosphere: 255 DEG C keep the temperature 5.0 hours；280 DEG C keep the temperature 3.0 hours；335 DEG C of guarantors
Temperature 12.0 hours；375 DEG C keep the temperature 3.0 hours, cool to room temperature after solidification with the furnace to get o-phthalonitrile resin is arrived.Gu
Change product compared with the IR characteristic peak of raw material, is mainly shown as: the IR characteristic peak 2229cm of itrile group in o-phthalonitrile resin-1
It is apparent to weaken, almost disappear.Isoindoline 1660cm can be observed simultaneously-1Characteristic peak, but without triazine ring 1520
Or 1360cm-1Characteristic peak.The isothermal rheology test curve of curing system shows that the storage modulus of curing system before curing is equal
It is significantly less than 1.00Pa (0.00-1.00Pa), the storage modulus after solidification is above 0.1MPa.TGA:T5%: 486.6 DEG C；It is residual
Charcoal rate: 72.1%.In terms of comprehensive, a kind of adjacent benzene two for capableing of self-catalysis solidification and machinability and Good Heat-resistance is obtained
Formonitrile HCN resin.
Rheometer test: initial storage modulus: 0.07Pa be fully cured after storage modulus: 0.15MPa
TGA:T5%:486.6 DEG C of carbon yield: 72.1%.
Claims (4)
1. a kind of phthalonitrile monomer containing alkyl, structural formula are as follows:
In formula, R1For H, F, Cl, Br, I, CH3、CH2CH3、CH2CH2CH3、CH(CH3)2、CF3、OCH3、OCH2CH3、CH=CH2、C≡CH、C≡N、One of；
R2、R3、R4、R5And R6It can be the same or different, be H, F, Cl, Br, I, CH3、CH2CH3、CF3、OCH3、NO2、C≡N、
OH、One of.
2. the preparation method of the phthalonitrile monomer described in claim 1 containing alkyl, it is characterised in that steps are as follows:
(1) using two phenolic hydroxyl-compounds A, (3 or 4)-nitrophthalonitrile and catalyst B as raw material, two phenolic hydroxyl-compounds A
Molar ratio with (3 or 4)-nitrophthalonitrile is 1.0:(2.0~3.3), two phenolic hydroxyl-compounds A and catalyst B's rubs
You are than being 1.0:(1.0~1.5)；
Wherein the structure of two phenolic hydroxyl-compounds A is as follows:
Two phenolic hydroxyl-compounds A, (3 or 4)-nitrophthalonitrile are dissolved in polar solvent jointly, is added and urges into solution
Agent B, 20~40 DEG C insulation reaction 10~15 hours；After reaction, reaction solution is washed with deionized water and methanol respectively
Filter cake is washed at least twice and collects, by filtration cakes torrefaction to constant weight up to the phthalonitrile monomer containing alkyl, structural formula is as follows:
In the step, the dosage of polar solvent is that the solid content in reaction solution is 10%~50%, the solid content=(diphenol hydroxyl
The quality of based compound A+(3 or 4)-nitrophthalonitrile quality): polar solvent volume, two phenolic hydroxyl-compounds A and (3
Or 4)-nitrophthalonitrile mass unit is gram, the volume unit of polar solvent is milliliter；
In the structural formula of the two phenolic hydroxyl-compounds A and the phthalonitrile monomer containing alkyl, R1For H, F, Cl, Br, I,
CH3、CH2CH3、CH2CH2CH3、CH(CH3)2、C(CH3)3、CF3、OCH3、OCH2CH3、 CH=CH2、C≡CH、C
≡N、One of.R2、R3、R4、R5And R6Can be the same or different, be H, F, Cl, Br, I,
CH3、CH2CH3、C(CH3)3、CF3、OCH3、NO2、C≡N、OH、One of；
The general formula of synthesis process are as follows:
In above-mentioned synthesis process, the catalyst B is sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, sodium hydroxide, hydrogen-oxygen
Change one of potassium.The polar solvent is N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), pregnancy
One of base phosphoric triamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone (NMP).
3. the phthalonitrile monomer described in claim 1 containing alkyl is preparing the application in o-phthalonitrile resin.
4. the phthalonitrile monomer containing alkyl is preparing the application in o-phthalonitrile resin according to claim 3,
It is characterized in that successively being solidified the phthalonitrile monomer for containing alkyl (in described below according to following temperature and soaking time
Temperature is represented with T): 0.0~5.0 hour is kept the temperature at 260 DEG C of 220≤T <；0.0~5.0 hour is kept the temperature at 310 DEG C of 260≤T <；
0.5~24.0 hour is kept the temperature at 350 DEG C of 310≤T <；0.0~10.0 hour is kept the temperature at 350≤T≤400 DEG C；After solidification
Room temperature is cooled to the furnace to get o-phthalonitrile resin is arrived.
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| CN111517989A (en) * | 2019-06-12 | 2020-08-11 | 四川大学 | Alkyl-containing phthalonitrile resin based on autocatalytic curing and preparation method thereof |
| CN113402423A (en) * | 2021-05-31 | 2021-09-17 | 四川大学 | Phthalonitrile monomer containing parylene structure, phthalonitrile resin and preparation method thereof |
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| CN112521326B (en) * | 2020-11-17 | 2022-07-26 | 四川大学 | Phenolic compound containing tyramine structure, phthalonitrile, and preparation method and application thereof |
| CN114349954B (en) * | 2021-12-31 | 2023-11-21 | 四川大学 | Phthalonitrile-terminated polyaryl ether nitrile containing methylene/methylene, crosslinked cured modified polyaryl ether nitrile and preparation method thereof |
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