CN111517989B - Self-catalytic curing-based resin containing alkyl phthalonitrile and preparation method thereof - Google Patents
Self-catalytic curing-based resin containing alkyl phthalonitrile and preparation method thereof 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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Abstract
The invention discloses an alkyl-containing phthalonitrile resin based on autocatalytic curing and a preparation method thereof, wherein the alkyl-containing phthalonitrile resin is formed by curing an alkyl-containing phthalonitrile monomer with autocatalytic and autocatalytic characteristics as a raw material, and the structural formula of the monomer is as follows:
the invention takes the monomer containing alkyl phthalonitrile as raw material, and because the alkyl group is introduced as a catalytic unit, the monomer can provide active hydrogen proton to initiate the crosslinking of cyano group, thus realizing the autocatalytic curing of the monomer and obviously improving the curing rate of the monomer. The prepared resin containing the alkyl phthalonitrile shows excellent thermal stability and thermal oxygen stability.
Description
Technical Field
The invention belongs to the technical field of phthalonitrile resin, and relates to a phthalonitrile resin prepared from an alkyl-containing phthalonitrile monomer with self-catalysis and curing characteristics as a raw material and a preparation method thereof.
Background
Phthalonitrile resin has high thermal stability, thermal oxygen stability, low flammability, chemical corrosion resistance and excellent high-temperature mechanical properties, and is widely used as matrix resin of high-performance composite materials in the high-tech fields of aerospace and the like.
The phthalonitrile resin is formed by curing a phthalonitrile monomer. However, in the existing phthalonitrile resin preparation process, if a curing agent is not added, the curing of the phthalonitrile monomer is an extremely slow process (generally, the viscosity cannot be obviously increased for more than one week at 300 ℃), so that the processing is difficult, the processing cost is high, and the application of the resin is further limited. The addition of the curing agent can raise the curing speed of phthalonitrile resin to a certain extent, and at the same time, can reduce its curing condition, and can be used as curing agent for quick curing of phthalonitrile resin, etc. the aromatic amine, phenolic hydroxyl group, organic acid, ammonium salt and Lewis acid base of metal salt, etc. can promote quick curing of phthalonitrile resin, but in the course of curing, the small-molecular curing agent can be inevitably volatilized, so that the material has defects, and its service performance is reduced (Sastra S B, keller T M.Phthalonile cure reaction with aromatic diamines [ J ] Journal of Polymer Science Part A: polymer Chemistry,1998,36 (11): 1885-1890.).
The problems can be effectively solved by introducing active groups such as phenolic hydroxyl, primary ammonia, secondary amine and the like into the phthalonitrile monomer structure to form an autocatalytic curing system. However, the phthalonitrile resin structure obtained by catalysis of phenolic hydroxyl groups, primary ammonia and secondary amine contains triazine rings, isoindoline and phthalocyanine, the resin structure is complex and difficult to regulate, and the conversion rate of nitrile groups is reduced. In addition, the synthesis and purification of the above-mentioned autocatalytic phthalonitrile monomers formed by introducing active groups such as phenolic hydroxyl groups, primary amines, secondary amines and the like are often relatively complex (HuJ, 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.), and the synthesis of the monomers usually comprises a plurality of stages of reactions, and the purification thereof often requires further recrystallization on the basis of methanol filtration and washing, which increases the preparation cost of the phthalonitrile resin and further limits the wide range of applications thereof.
In summary, if the phthalonitrile monomer is modified, the curing of the phthalonitrile resin can be accelerated without adding other curing agents, and meanwhile, the introduction of groups with complex structures and difficult to regulate and control is avoided, and the preparation cost of the phthalonitrile resin is further reduced, so that the method is an important point and a difficult point of the research of the phthalonitrile resin in the prior art.
Disclosure of Invention
Aiming at overcoming the defects of the prior art and further improving the development level of phthalonitrile resin materials, the invention provides the alkyl-containing phthalonitrile resin prepared by taking the alkyl-containing phthalonitrile monomer with self-catalysis and self-curing characteristics as the raw material and the preparation method thereof, so that the phthalonitrile resin with excellent thermal stability and thermal oxygen stability and better structure controllability can be obtained by curing under the condition of no adding curing agent, the curing rate is obviously improved, and the preparation period of the phthalonitrile resin is shortened.
The alkyl-containing phthalonitrile resin based on autocatalysis curing is formed by curing an alkyl-containing phthalonitrile monomer with autocatalysis and autoclaving characteristics as a raw material, and the structural general formula of the alkyl-containing phthalonitrile monomer with autocatalysis and autoclaving characteristics is as follows:
Wherein R is 1 is-H, -F, -Br, -I, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-C(CH 3 ) 3 、-CF 3 、-OCH 3 、-OCH 2 CH 3 、
-C≡N、/>
One of the following; wherein the method comprises the steps of
Any carbon on the ring as grafting site, +.>
Any carbon on the benzene ring without cyano group is used as grafting site;
R 2 、R 3 、R 4 and R is 5 Identical or different, are-H, -F, -Br, -I, -C (CH) 3 ) 3 、-CH 2 CH 3 、-CF 3 、-OCH 3 、-NO 2 、-C≡N、
One of the following; wherein->
Any carbon on the ring serves as a grafting site.
The invention further provides a preparation method of the resin containing the alkyl phthalonitrile based on autocatalysis curing, which is obtained by taking the monomer containing the alkyl phthalonitrile with autocatalysis and autocatalysis characteristics as a raw material for curing, and comprises the following specific steps: the alkyl phthalonitrile-containing monomer with self-catalysis and self-curing characteristics is subjected to curing operation in an inert gas atmosphere according to the following temperature gradient and time:
preserving heat for 0-5 hours at the temperature of T being more than or equal to 220 and less than 260 ℃;
preserving heat for 0-6 hours at the temperature of T being more than or equal to 260 and less than 310 ℃;
preserving heat for 0.5-24 hours at the temperature of T being more than or equal to 310 and less than 350 ℃;
the temperature is 220-260 ℃ and the heat preservation time is 260-310 ℃ and is not 0 at the same time;
or the phthalonitrile monomer is solidified in inert gas atmosphere according to the following temperature gradient and time:
Preserving heat for 0-5 hours at the temperature of T being more than or equal to 220 and less than 260 ℃;
preserving heat for 0-6 hours at the temperature of T being more than or equal to 260 and less than 310 ℃;
preserving heat for 0.5-24 hours at the temperature of T being more than or equal to 310 and less than 350 ℃;
keeping the temperature at the temperature of more than or equal to 350 and less than or equal to 400 ℃ for 2 to 10 hours;
the temperature is 220-260 ℃ and the heat preservation time is 260-310 ℃ and is not 0 at the same time;
and after the solidification is finished, cooling the obtained product to room temperature along with a furnace to obtain the resin containing the alkyl phthalonitrile.
In a preferred implementation, the alkyl-containing phthalonitrile monomer is subjected to a curing operation in an inert gas atmosphere according to the following temperature gradient and time:
preserving heat for 0-5 hours at the temperature of T being more than or equal to 220 and less than 260 ℃;
preserving heat for 3-6 hours at the temperature of T being more than or equal to 260 and less than 310 ℃;
preserving heat for 8.5-17 hours at the temperature of T being more than or equal to 310 and less than 350 ℃;
or the phthalonitrile monomer is solidified in inert gas atmosphere according to the following temperature gradient and time:
preserving heat for 0-5 hours at the temperature of T being more than or equal to 220 and less than 260 ℃;
preserving heat for 3-6 hours at the temperature of T being more than or equal to 260 and less than 310 ℃;
preserving heat for 8.5-17 hours at the temperature of T being more than or equal to 310 and less than 350 ℃;
Keeping the temperature at the temperature of more than or equal to 350 and less than or equal to 400 ℃ for 2 to 6 hours;
and after the solidification is finished, cooling the obtained product to room temperature along with a furnace to obtain the resin containing the alkyl phthalonitrile.
The preparation method of the resin containing the alkyl phthalonitrile with the self-catalysis and self-curing characteristics comprises the following steps of:
the preparation method is characterized by taking a diphenol hydroxyl compound and (3 or 4) -nitrophthalonitrile as raw materials and carrying out nucleophilic substitution reaction, and comprises the following specific steps: dissolving a diphenol hydroxyl compound, (3 or 4) -nitrophthalonitrile in a polar solvent, adding a catalyst into the obtained solution, and then carrying out heat preservation reaction for 10-15 hours at 20-40 ℃ to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, and washing and drying the solid reaction product to constant weight to obtain an alkyl phthalonitrile-containing monomer; the mol ratio of the diphenol hydroxyl compound to the (3 or 4) -nitrophthalonitrile to the catalyst is 1.0: (2.2-3.3): (1.0 to 1.2); the structural general formula of the diphenol hydroxyl compound is as follows:
wherein R is 1 is-H, -F, -Br, -I, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-C(CH 3 ) 3 、-CF 3 、-OCH 3 、-OCH 2 CH 3 、
-C≡N、/>
One of the following; wherein the method comprises the steps of
Any carbon on the ring as grafting site, +. >
Any carbon on the benzene ring without cyano group is used as grafting site;
R 2 、R 3 、R 4 and R is 5 Identical or different, are-H, -F, -Br, -I, -C (CH) 3 ) 3 、-CH 2 CH 3 、-CF 3 、-OCH 3 、-NO 2 、-C≡N、
One of the following; wherein->
Any carbon on the ring serves as a grafting site.
In the preparation of the monomer containing the alkyl phthalonitrile, the polar solution is one of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), hexamethylphosphoric triamide, dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP). The polar solvent is used in an amount that at least the diphenol hydroxyl compound and the (3 or 4) -nitrophthalonitrile are completely dissolved.
In the preparation of the monomer containing the alkyl phthalonitrile, the catalyst is used for catalyzing nucleophilic substitution reaction between the nitro and the hydroxyl. The catalyst is one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide.
In the preparation of the monomer containing the alkyl phthalonitrile, the obtained reaction liquid containing the solid reaction product is filtered to obtain the solid reaction product, the solid reaction product is washed by deionized water and methanol in sequence to remove unreacted raw material diphenol hydroxyl compound, (3 or 4) -nitrophthalonitrile and catalyst attached to the surface, each washing liquid is washed at least twice, the obtained solid reaction product is collected, and the solid reaction product is dried to constant weight within 100 ℃ to obtain the monomer containing the alkyl phthalonitrile.
The preparation method of the alkyl phthalonitrile-containing resin with self-catalysis and self-curing characteristics is characterized in that the temperature is kept for 0-5 hours at 220-260 ℃ and 0-6 hours at 260-310 ℃, and the two stages are pre-curing stages, so that the interference of small molecular substances possibly remained on the curing morphology of the product is prevented. Preserving heat for 0.5-24 hours at the temperature of 310-350 ℃ and preserving heat for 2-10 hours at the temperature of 350-400 ℃ which are post-curing stages to further improve the crosslinking degree. In a preferred implementation, to avoid oxidative interference of oxygen at the preparation temperature, the alkyl phthalonitrile-containing monomer is preferably cured under nitrogen.
According to the preparation method of the alkyl-containing phthalonitrile resin with the self-catalysis and self-curing characteristics, as the alkyl group can provide active hydrogen protons to trigger cyano reaction, the alkyl-containing phthalonitrile monomer can be cured under the condition of not adding a curing agent; in addition, due to the participation of active hydrogen protons in the introduced alkyl groups, crosslinking of cyano groups in the alkyl phthalonitrile-containing monomer can be accelerated, thereby improving the curing rate.
The alkyl-containing phthalonitrile resin prepared by the method can be highly crosslinked in a relatively short time, so that the phthalonitrile resin shows excellent thermal stability and thermo-oxidative stability; in addition, in the resin structure, the cyano cross-linking system mainly takes the isoindoline structure as a main part, and does not contain a triazine ring structure, so that the controllability of the obtained resin structure is improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention discovers the autocatalytic curing performance of the monomer containing the alkyl phthalonitrile, prepares the phthalonitrile resin by taking the monomer containing the alkyl phthalonitrile as a raw material for the first time under the condition of no addition of a curing agent, and provides a new technical scheme for preparing the phthalonitrile resin without the addition of the curing agent;
2. according to the invention, the alkyl-containing phthalonitrile monomer is used as a raw material, and the alkyl group is introduced as a catalytic unit, so that active hydrogen protons can be provided to initiate the crosslinking of the cyano group, thus the self-catalytic curing of the monomer can be realized to form the phthalonitrile resin, the curing rate of the monomer is obviously improved, and the preparation period of the phthalonitrile resin is shortened;
3. according to the invention, the monomer containing the alkyl phthalonitrile is used as a raw material, the curing is realized through the alkyl on the main chain of the monomer, and an active group with autocatalytic curing is not required to be additionally designed and introduced, so that the production cost of the phthalonitrile resin can be greatly reduced;
4. since the alkyl structure widely exists in various types of small molecules and polymers, such as in nature, a large amount of alkyl structures exist in cellulose and lignin, and a large amount of alkyl structures exist in artificially synthesized small molecules and polymers, the raw material range of the phthalonitrile resin can be greatly widened, and particularly the alkyl-containing bio-based structure and petroleum-based structure can exert higher value;
5. The invention takes the monomer containing alkyl phthalonitrile as raw material, and the polarity of the alkyl is lower, which is favorable for controlling the water absorption rate of the phthalonitrile resin and reducing the dielectric constant of the cured product, thus being favorable for expanding the application of the phthalonitrile resin in low dielectric constant materials;
6. the phthalonitrile resin prepared by the invention has excellent thermal stability and thermo-oxidative stability, which shows that the phthalonitrile resin has higher crosslinking density, thereby leading the phthalonitrile resin to have good mechanical properties;
7. the alkyl phthalonitrile-containing resin prepared by the invention has no small molecular catalyst or curing agent, so that the defect of air bubbles and air holes caused by volatilization of small molecules is avoided, and the mechanical property of the resin can be further improved;
8. the prepared resin containing the alkyl phthalonitrile does not contain a triazine ring structure, and the structure mainly takes isoindoline as a main component, so that the controllability of the product structure is improved;
9. the preparation method of the monomer containing the alkyl phthalonitrile can be realized through one-step nucleophilic substitution reaction, so that the preparation process is simple, the reaction condition is mild, and the preparation method is suitable for industrial production.
Drawings
FIG. 1 is an infrared spectrum of the corresponding products of bisphenol F type phthalonitrile prepared in example 1 before and after curing.
FIG. 2 is an isothermal rheology diagram of bisphenol F type phthalonitrile monomer prepared in example 1 at 310 ℃.
FIG. 3 is a thermogravimetric plot of the corresponding products of bisphenol F type phthalonitrile prepared in example 1 before and after curing.
FIG. 4 is an isothermal rheology at 310℃of a bisphenol-derived, alkyl-free phthalonitrile monomer prepared in comparative example 1.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully by way of example only, and not all embodiments of the invention. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the invention, are within the scope of the invention.
In the following examples:
(1) 1 HNMR test, i.e. nuclear magnetic resonance hydrogen spectrum @, of 1 H NMR) was obtained by testing with Bruker Avance-400 NMR instrument, germany, with the solvent DMSO-d6 or CDCl 3 。
(2) Infrared spectroscopy (FTIR) was performed using potassium bromide (KBr) tabletting and on a Nicolet FTIR-460 fourier transform infrared spectrometer in the united states.
(3) The storage modulus in the rheological test data was obtained by plate (diameter 25 mm) rotational rheometer testing.
(4) TGA, T5%: refers to the temperature at which the sample loses 5% weight in a thermogravimetric analyzer TG at a temperature rise rate of 10 ℃/min under nitrogen atmosphere.
(5) Carbon residue refers to the residual weight of the sample in the thermogravimetric analyzer TG when it reaches 800 ℃.
Example 1
(1) Preparation of bisphenol F-derived phthalonitrile monomers
In the embodiment, bisphenol F (CAS number: 620-92-8) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the bisphenol F (CAS number: 620-92-8), the 4-nitrophthalonitrile and the potassium carbonate is 1.0:2.3:1.1, the using amount of the bisphenol F is 3.01g, and the structural formula of the bisphenol F is as follows:
bisphenol F and 4-nitrophthalonitrile are dissolved in 20mL of NMP solvent, then potassium carbonate is added into the obtained solution, and the reaction is carried out for 12 hours at 30 ℃ under the condition of heat preservation, thus obtaining a reaction solution containing solid reaction products; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product to constant weight at 100 ℃ to obtain the bisphenol F-derived phthalonitrile monomer.
The obtained bisphenol F-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: preserving heat for 5h at 250 ℃, preserving heat for 3.5h at 280 ℃, preserving heat for 12h at 310 ℃ and preserving heat for 3h at 370 ℃, and cooling to room temperature along with a furnace after solidification is finished, thus obtaining the resin containing the alkyl phthalonitrile.
The resulting bisphenol F-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) were subjected to infrared analysis, and the results are shown in FIG. 1. As can be seen from FIG. 1, the characteristic peak of nitrile group was 2229cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1660cm can be observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
The resulting bisphenol F-derived phthalonitrile monomer was subjected to isothermal rheology at 310℃and the results are shown in FIG. 2. As can be seen from FIG. 2, the storage modulus of the obtained cured system before curing is significantly less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.07Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing Storage modulus, 0.15MPa. The large difference in front and back storage modulus reflects that the system has significant autocatalytic curing behavior. The resulting bisphenol F-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) were subjected to thermogravimetric analysis, and the analysis results are shown in FIG. 3. As can be seen from FIG. 3, the fully cured phthalonitrile resin prepared had a temperature (T 5％ ) 486.6 ℃; the carbon residue rate at 800 ℃ is 72.1 percent. From this, it can be seen that in this example, the phthalonitrile resin having excellent heat resistance was prepared from the alkyl-containing phthalonitrile monomer as a raw material by self-autocatalytic curing.
Comparative example 1
The applicant has found that phthalonitrile monomers containing no alkyl structure do not have an autocatalytic self-curing effect. The following reaction was carried out using dihydric phenol (CAS number 92-88-6) as a starting material in accordance with the method for preparing monomers and resins given in example 1, and the resulting products were analyzed as follows:
(1) In the example, dihydric phenol (CAS number: 92-88-6) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 3.2g, and the structural formula of the dihydric phenol is as follows:
Dissolving dihydric phenol and 4-nitrophthalonitrile in 25mL of NMP solvent, adding potassium carbonate into the obtained solution, and then carrying out heat preservation reaction at 30 ℃ for 10 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product to constant weight at 100 ℃ to obtain the dihydric phenol-derived phthalonitrile monomer without alkyl.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) The phthalonitrile monomer prepared in the step (1) is subjected to heat preservation operation in a nitrogen atmosphere according to the following temperature gradient: preserving heat for 5h at 250 ℃, preserving heat for 3.5h at 280 ℃, preserving heat for 12h at 310 ℃ and preserving heat for 3h at 370 ℃, and cooling to room temperature along with a furnace after the heat preservation is finished.
Carrying out infrared analysis on the dihydric phenol derived and non-alkyl phthalonitrile monomer (before curing) obtained in the step (1) and the product obtained in the step (2), wherein the characteristic peak of nitrile group is 2229cm -1 There was no significant decrease, indicating that the nitrile groups may not undergo a cross-linking curing reaction. At the same time, no isoindoline 1660cm was observed -1 And 1090cm -1 The characteristic peaks of (2) indicate that the prepared phthalonitrile monomer without alkyl group has no self-catalytic self-curing effect and cannot obtain phthalonitrile resin.
Isothermal rheology tests were performed at 310 ℃ on the resulting dihydric phenol-derived, alkyl-free phthalonitrile monomer, and the resulting system was isothermal at 310 ℃ for 3 hours without any increase in viscosity of the system, as shown in fig. 4, again indicating that the alkyl-free phthalonitrile monomer did not exhibit self-catalyzed curing behavior.
Example 2
(1) Preparation of dihydric phenol derived phthalonitrile monomers
In the embodiment, dihydric phenol (CAS number: 2081-08-05) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 3.2g, and the structural formula of the dihydric phenol is as follows:
dissolving dihydric phenol and 4-nitrophthalonitrile in 25mL of NMP solvent, adding potassium carbonate into the obtained solution, and then carrying out heat preservation reaction at 30 ℃ for 10 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 100 ℃ to constant weight to obtain the dihydric phenol-derived phthalonitrile monomer.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: preserving heat for 4.5h at 230 ℃, preserving heat for 3h at 270 ℃, preserving heat for 8.5h at 320 ℃ and preserving heat for 3h at 375 ℃, and cooling to room temperature along with a furnace after solidification is finished, thus obtaining the resin containing the alkyl phthalonitrile.
Infrared analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out, with a characteristic peak of nitrile group of 2229cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1660cm can be observed -1 And 1090cm -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from dihydric phenol at 310 ℃, and the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.06Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.21MPa. Thermogravimetric analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out to prepare a phthalonitrile resin having a weight loss of 5% (T) 5％ ) The temperature at that time was 470.6 ℃; residue (C)The char yield was 71.5%. In the embodiment, the phthalonitrile resin with excellent heat resistance is prepared by taking the monomer containing alkyl phthalonitrile as a raw material and utilizing self-autocatalytic curing.
Example 3
(1) Preparation of dihydric phenol derived phthalonitrile monomers
In the embodiment, dihydric phenol (CAS number: 1576-13-2) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 3.3g, and the structural formula of the dihydric phenol is as follows:
dissolving dihydric phenol and 4-nitrophthalonitrile in 26mL of DMSO solvent, adding potassium carbonate into the obtained solution, and then carrying out heat preservation reaction at 25 ℃ for 15 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 100 ℃ to constant weight to obtain the dihydric phenol-derived phthalonitrile monomer.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: preserving heat for 3h at 240 ℃, preserving heat for 4.5h at 265 ℃, preserving heat for 11h at 330 ℃ and preserving heat for 3.5h at 360 ℃, and cooling to room temperature along with a furnace after solidification is finished, thus obtaining the resin containing the alkyl phthalonitrile.
Ortho-position derived from the obtained dihydric phenolThe phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) were subjected to infrared analysis, and the characteristic peak of nitrile group was 2229cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1090cm can be observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from the dihydric phenol at 310 ℃, and the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.05Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.23MPa. Thermogravimetric analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out to prepare a phthalonitrile resin having a weight loss of 5% (T) 5％ ) The temperature at that time was 459.5 ℃; the carbon residue rate was 71.2%. From this, it can be seen that in this example, the phthalonitrile resin having excellent heat resistance was prepared from the alkyl-containing phthalonitrile monomer as a raw material by self-autocatalytic curing.
Example 4
(1) Preparation of dihydric phenol derived phthalonitrile monomers
In the embodiment, dihydric phenol (CAS number: 1769-01-1) and 4-nitrophthalonitrile are used as raw materials, sodium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the sodium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 4.5g, and the structural formula of the dihydric phenol is as follows:
dissolving dihydric phenol and 4-nitrophthalonitrile in 30mL of DMSO solvent, adding sodium carbonate into the obtained solution, and then carrying out heat preservation reaction at 35 ℃ for 13 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 100 ℃ to constant weight to obtain the dihydric phenol-derived phthalonitrile monomer.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: heat preservation is carried out for 3.5h at 255 ℃, 3.0h at 280 ℃, 15.0h at 320 ℃ and 4.5h at 370 ℃, and after solidification, the mixture is cooled to room temperature along with a furnace, thus obtaining the resin containing the alkyl phthalonitrile.
Infrared analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out, and the characteristic peak of nitrile group was 2231cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1092cm can be observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from the dihydric phenol at 310 ℃, and the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.08Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.31MPa. Thermogravimetric analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out to prepare a phthalonitrile resin having a weight loss of 5% (T) 5％ ) The temperature at the time is 475.2 ℃; the carbon residue rate was 71.6%. From this, it can be seen that the embodiment uses the monomer containing alkyl phthalonitrile as raw material, and prepares the o-phthalonitrile with excellent heat resistance by self-catalyzed curingPhthalonitrile resin.
Example 5
(1) Preparation of dihydric phenol derived phthalonitrile monomers
In the embodiment, dihydric phenol (CAS number: 52173-65-6) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 4.8g, and the structural formula of the dihydric phenol is as follows:
dissolving dihydric phenol and 4-nitrophthalonitrile in 35mL of DMSO solvent, adding potassium carbonate into the obtained solution, and then carrying out heat preservation reaction at 25 ℃ for 11 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain solid filtering, washing with deionized water and methanol (washing with each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 100 ℃ to constant weight to obtain the dihydric phenol-derived phthalonitrile monomer.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: preserving heat for 5.0h at 235 ℃, preserving heat for 4.0h at 290 ℃, preserving heat for 14.5h at 335 ℃ and preserving heat for 3.5h at 380 ℃, and cooling to room temperature along with a furnace after solidification is finished, thus obtaining the resin containing the alkyl phthalonitrile.
Infrared analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out, and the characteristic peak of nitrile group was 2231cm -1 Obvious weakening, almostComplete disappearance indicates that the nitrile groups have largely and even completely participated in the crosslinking reaction. At the same time, isoindoline 1089cm was observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from dihydric phenol at 310 ℃, the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.1Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.18MPa. Thermogravimetric analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out to prepare a phthalonitrile resin having a weight loss of 5% (T) 5％ ) The temperature at that time was 462.3 ℃; the carbon residue rate is 70.6%. From this, it can be seen that in this example, the phthalonitrile resin having excellent heat resistance was prepared from the alkyl-containing phthalonitrile monomer as a raw material by self-autocatalytic curing.
Example 6
(1) Preparation of dihydric phenol derived phthalonitrile monomers
In the embodiment, dihydric phenol (CAS number: 103330-88-7) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 5.0g, and the structural formula of the dihydric phenol is as follows:
dissolving dihydric phenol and 4-nitrophthalonitrile in 45mL of DMSO solvent, adding potassium carbonate into the obtained solution, and then carrying out heat preservation reaction at 28 ℃ for 11 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 100 ℃ to constant weight to obtain the dihydric phenol-derived phthalonitrile monomer.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: heat preservation is carried out for 2.0h at 250 ℃, 3.5h at 280 ℃, 17.0h at 315 ℃ and 2.0h at 385 ℃, and after solidification, the mixture is cooled to room temperature along with a furnace, thus obtaining the resin containing the alkyl phthalonitrile.
Infrared analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out, and the characteristic peak of nitrile group was 2231cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1090cm can be observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from the dihydric phenol at 310 ℃, and the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.07Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.18MPa. Thermogravimetric analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out to prepare a phthalonitrile resin having a weight loss of 5% (T) 5％ ) The temperature at that time was 457.3 ℃; the carbon residue rate is 70.8%. From this, it can be seen that in this example, the phthalonitrile resin having excellent heat resistance was prepared from the alkyl-containing phthalonitrile monomer as a raw material by self-autocatalytic curing.
Example 7
(1) Preparation of dihydric phenol derived phthalonitrile monomers
In the embodiment, dihydric phenol (CAS number: 93006-77-0) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 4.0g, and the structural formula of the dihydric phenol is as follows:
dissolving dihydric phenol and 4-nitrophthalonitrile in 35mL of DMSO solvent, adding potassium carbonate into the obtained solution, and then carrying out heat preservation reaction at 32 ℃ for 13 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 100 ℃ to constant weight to obtain the dihydric phenol-derived phthalonitrile monomer.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: the temperature is kept for 4.0h at 260 ℃, 5.0h at 285 ℃, 11.5h at 340 ℃ and 6.0h at 385 ℃, and the resin containing the alkyl phthalonitrile is obtained after cooling to room temperature along with a furnace after solidification.
Infrared analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out, and the characteristic peak of nitrile group was 2230cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1090cm can be observed -1 Is of (1)Peak sign, but at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from the dihydric phenol at 310 ℃, and the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.11Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.24MPa. Thermogravimetric analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out to prepare a phthalonitrile resin having a weight loss of 5% (T) 5％ ) The temperature at that time was 467.4 ℃; the carbon residue rate was 71.5%. From this, it can be seen that in this example, the phthalonitrile resin having excellent heat resistance was prepared from the alkyl-containing phthalonitrile monomer as a raw material by self-autocatalytic curing.
Example 8
(1) Preparation of dihydric phenol derived phthalonitrile monomers
In the embodiment, dihydric phenol (CAS number: 10218-59-4) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 4.8g, and the structural formula of the dihydric phenol is as follows:
dissolving dihydric phenol and 4-nitrophthalonitrile in 35mL of DMSO solvent, adding potassium carbonate into the obtained solution, and then carrying out heat preservation reaction at 20 ℃ for 13 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 100 ℃ to constant weight to obtain the dihydric phenol-derived phthalonitrile monomer.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis, the resulting structural formulaThe following are provided:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: preserving heat for 5.0h at 240 ℃, preserving heat for 3.0h at 280 ℃, preserving heat for 16h at 310 ℃ and preserving heat for 3.5h at 350 ℃, and cooling to room temperature along with a furnace after solidification is finished, thus obtaining the resin containing the alkyl phthalonitrile.
Infrared analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out, with a characteristic peak of nitrile group of 2229cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1090cm can be observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from dihydric phenol at 310 ℃, and the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.12Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.18MPa. Thermogravimetric analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out to prepare a phthalonitrile resin having a weight loss of 5% (T) 5％ ) The temperature at that time was 451.2 ℃; the carbon residue rate is 70.2%. From this, it can be seen that in this example, the phthalonitrile resin having excellent heat resistance was prepared from the alkyl-containing phthalonitrile monomer as a raw material by self-autocatalytic curing.
Example 9
(1) Preparation of dihydric phenol derived phthalonitrile monomers
In the embodiment, dihydric phenol (CAS number: 13004-51-8) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 5.8g, and the structural formula of the dihydric phenol is as follows:
dissolving dihydric phenol and 4-nitrophthalonitrile in 45mL of DMAC solvent, adding potassium carbonate into the obtained solution, and then carrying out heat preservation reaction at 40 ℃ for 13 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 100 ℃ to constant weight to obtain the dihydric phenol-derived phthalonitrile monomer.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: preserving heat for 5.0h at 280 ℃, preserving heat for 15h at 310 ℃ and preserving heat for 6.0h at 375 ℃, and cooling to room temperature along with a furnace after solidification is finished, thus obtaining the resin containing the alkyl phthalonitrile.
Infrared analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out, and the characteristic peak of nitrile group was 2230cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1091cm can be observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
For the second obtainedIsothermal rheological test is carried out on the catechol-derived phthalonitrile monomer at 310 ℃, and the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.06Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.31MPa. Thermogravimetric analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out to prepare a phthalonitrile resin having a weight loss of 5% (T) 5％ ) The temperature at that time is 494.2 ℃; the carbon residue rate was 73.1%. From this, it can be seen that in this example, the phthalonitrile resin having excellent heat resistance was prepared from the alkyl-containing phthalonitrile monomer as a raw material by self-autocatalytic curing.
Example 10
(1) Preparation of dihydric phenol derived phthalonitrile monomers
In the embodiment, dihydric phenol (CAS number: 93717-58-9) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 3.5g, and the structural formula of the dihydric phenol is as follows:
dissolving dihydric phenol and 4-nitrophthalonitrile in 32mL of DMSO solvent, adding potassium carbonate into the obtained solution, and then carrying out heat preservation reaction at 40 ℃ for 15 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 100 ℃ to constant weight to obtain the dihydric phenol-derived phthalonitrile monomer.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: preserving heat for 5.0h at 240 ℃, preserving heat for 3.5h at 280 ℃, preserving heat for 13.5h at 310 ℃ and preserving heat for 3.0h at 390 ℃, and cooling to room temperature along with a furnace after solidification is finished, thus obtaining the resin containing the alkyl phthalonitrile.
Infrared analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out, and the characteristic peak of nitrile group was 2232cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1091cm can be observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from dihydric phenol at 310 ℃, and the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.09Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.42MPa. Thermogravimetric analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out to prepare a phthalonitrile resin having a weight loss of 5% (T) 5％ ) The temperature at that time was 507.3 ℃; the carbon residue rate was 73.5%. From this, it can be seen that a phthalonitrile resin which is capable of autocatalytically curing and is excellent in processability and heat resistance was prepared by this example.
Example 11
(1) Preparation of dihydric phenol derived phthalonitrile monomers
In the embodiment, dihydric phenol (CAS number: 4081-02-1) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 4.8g, and the structural formula of the dihydric phenol is as follows:
dissolving dihydric phenol and 4-nitrophthalonitrile in 40mL of DMSO solvent, adding potassium carbonate into the obtained solution, and then carrying out heat preservation reaction at 35 ℃ for 10 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 100 ℃ to constant weight to obtain the dihydric phenol-derived phthalonitrile monomer.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: preserving heat for 4.0h at 280 ℃, preserving heat for 14.0h at 330 ℃ and preserving heat for 6.0h at 380 ℃, and cooling to room temperature along with a furnace after solidification to obtain the resin containing the alkyl phthalonitrile.
Infrared analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out, and the characteristic peak of nitrile group was 2230cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1090cm can be observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from dihydric phenol at 310 ℃, and the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.09Pa;the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.22MPa. Thermogravimetric analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out to prepare a phthalonitrile resin having a weight loss of 5% (T) 5％ ) The temperature at that time was 496.2 ℃; the carbon residue rate was 71.8%. From this, it can be seen that in this example, the phthalonitrile resin having excellent heat resistance was prepared from the alkyl-containing phthalonitrile monomer as a raw material by self-autocatalytic curing.
Example 12
(1) Preparation of dihydric phenol derived phthalonitrile monomers
In the embodiment, dihydric phenol (CAS number: 10690-03-1) and 4-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of the dihydric phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:2.3:1.1, the consumption of the dihydric phenol is 5.6g, and the structural formula of the dihydric phenol is as follows:
dissolving dihydric phenol and 4-nitrophthalonitrile in 45mL of DMSO solvent, adding potassium carbonate into the obtained solution, and then carrying out heat preservation reaction for 15 hours at 35 ℃ to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 80 ℃ to constant weight to obtain the dihydric phenol-derived phthalonitrile monomer.
The obtained dihydric phenol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: preserving heat for 4.5h at 280 ℃, preserving heat for 14.5h at 340 ℃ and preserving heat for 5.0h at 385 ℃, and cooling to room temperature along with a furnace after solidification is finished, thus obtaining the resin containing the alkyl phthalonitrile.
Infrared analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out, and the characteristic peak of nitrile group was 2231cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1089cm was observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from the dihydric phenol at 310 ℃, and the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.13Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.23MPa. Thermogravimetric analysis of the obtained dihydric phenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out to prepare a phthalonitrile resin having a weight loss of 5% (T) 5％ ) The temperature at that time was 502.4 ℃; the carbon residue rate is 72.3%. From this, it can be seen that in this example, the phthalonitrile resin having excellent heat resistance was prepared from the alkyl-containing phthalonitrile monomer as a raw material by self-autocatalytic curing.
Example 13
(1) Preparation of a Triphenol-derived phthalonitrile monomer
In the embodiment, the ternary phenol (CAS number: 603-44-1) and 4-nitrophthalonitrile are used as raw materials, sodium carbonate is used as a catalyst, the molar ratio of the ternary phenol to the 4-nitrophthalonitrile to the potassium carbonate is 1.0:3.3:1.1, the using amount of the ternary phenol is 5.8g, and the structural formula of the ternary phenol is as follows:
dissolving the triphenol and the 4-nitrophthalonitrile in 45mL of DMSO solvent, adding sodium carbonate into the obtained solution, and then carrying out heat preservation reaction at 40 ℃ for 13 hours to obtain a reaction solution containing a solid reaction product; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product at 80 ℃ to constant weight to obtain the triphenol-derived phthalonitrile monomer.
The obtained catechol-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of resin containing alkyl phthalonitrile
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: heat preservation is carried out for 5.0h at 250 ℃, 6.0h at 280 ℃, 12.0h at 310 ℃ and 5.0h at 370 ℃, and after solidification, the mixture is cooled to room temperature along with a furnace, thus obtaining the resin containing the alkyl phthalonitrile.
Infrared analysis of the obtained triphenol-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing) was carried out, and the characteristic peak of nitrile group was 2230cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1090cm can be observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from the obtained ternary phenol at 310 ℃, the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.08Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.47MPa. Phthalonitrile monomer (before curing) derived from the obtained triphenols and phthalonitrile tree Thermogravimetric analysis of the fat (after curing) was carried out, and the weight loss of the prepared phthalonitrile resin was 5% (T) 5％ ) The temperature at the time is 517.5 ℃; the carbon residue rate was 74.2%. From this, it can be seen that in this example, the phthalonitrile resin having excellent heat resistance was prepared from the alkyl-containing phthalonitrile monomer as a raw material by self-autocatalytic curing.
Example 14
(1) Preparation of bisphenol F-derived phthalonitrile monomers
In the embodiment, bisphenol F (CAS number: 620-92-8) and 3-nitrophthalonitrile are used as raw materials, potassium carbonate is used as a catalyst, the molar ratio of bisphenol F to 3-nitrophthalonitrile to potassium carbonate is 1.0:2.2:1.2, the dosage of bisphenol F is 3.32g, and the structural formula of bisphenol F is as follows:
bisphenol F and 3-nitrophthalonitrile are dissolved in 20mL of NMP solvent, then potassium carbonate is added into the obtained solution, and the reaction is carried out for 10 hours at the temperature of 32 ℃ to obtain a reaction solution containing solid reaction products; filtering the obtained reaction liquid to obtain a solid reaction product, washing the solid reaction product with deionized water and methanol (washing each washing liquid twice), collecting the obtained solid reaction product, and drying the solid reaction product to constant weight at 100 ℃ to obtain the bisphenol F-derived phthalonitrile monomer.
The obtained bisphenol F-derived phthalonitrile monomer is prepared by 1 H-NMR analysis gave the following structural formula:
(2) Preparation of phthalonitrile resin
And (3) curing the alkyl phthalonitrile-containing monomer prepared in the step (1) in a nitrogen atmosphere sequentially according to the following temperature gradient: preserving heat for 5h at 255 ℃, preserving heat for 3h at 280 ℃, preserving heat for 12h at 335 ℃ and preserving heat for 3h at 370 ℃, and cooling to room temperature along with a furnace after solidification is finished, thus obtaining the phthalonitrile resin.
Infrared analysis was performed on the obtained bisphenol F-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing), and the characteristic peak of nitrile group was 2229cm -1 The marked weakening, almost complete disappearance, indicates that the nitrile groups have been largely or even completely involved in the crosslinking reaction. At the same time, isoindoline 1660cm can be observed -1 But at 1520 or 1360cm -1 The characteristic peak is not generated, which indicates that the prepared phthalonitrile resin has no triazine ring structure.
Isothermal rheological test is carried out on the phthalonitrile monomer derived from bisphenol F at 310 ℃, the storage modulus of the obtained curing system before curing is obviously less than 1.00Pa (0.01-1.00 Pa), and the initial storage modulus before curing is 0.07Pa; the storage modulus after curing is higher than 0.1MPa, and the storage modulus after complete curing is 0.15MPa. Performing thermogravimetric analysis on the obtained bisphenol F-derived phthalonitrile monomer (before curing) and phthalonitrile resin (after curing), and obtaining phthalonitrile resin with 5% weight loss (T) 5％ ) The temperature at that time was 486.6 ℃; the carbon residue rate is 72.1%. From this, it can be seen that in this example, the phthalonitrile resin having excellent heat resistance was prepared from the alkyl-containing phthalonitrile monomer as a raw material by self-autocatalytic curing.
Claims (1)
1. The alkyl-containing phthalonitrile resin based on autocatalytic curing is characterized by being formed by curing an alkyl-containing phthalonitrile monomer with autocatalytic and self-curing characteristics as a raw material, wherein the structural general formula of the alkyl-containing phthalonitrile monomer with autocatalytic and self-curing characteristics is as follows:
wherein R is 1 is-F, -Br, -I, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-C(CH 3 ) 3 、-CF 3 、-OCH 3 、-OCH 2 CH 3 、
-C≡N、/>
One of the following; wherein->
Any carbon on the ring as grafting site, +.>
Any carbon on the benzene ring without cyano group is used as grafting site;
R 2 、R 3 、R 4 and R is 5 Identical or different, are-H, -F, -Br, -I, -C (CH) 3 ) 3 、-CH 2 CH 3 、-CF 3 、-OCH 3 、-NO 2 One of-C.ident.N.
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| CN102659628A (en) * | 2012-04-26 | 2012-09-12 | 四川大学 | Phthalonitrile monomer containing aromatic polyamide, synthetizing method thereof and poly phthalonitrile resin produced through solidification of phthalonitrile monomer |
| CN107810177A (en) * | 2015-05-22 | 2018-03-16 | 株式会社Lg化学 | Phthalonitrile compound |
| CN108290830A (en) * | 2015-12-02 | 2018-07-17 | 株式会社Lg化学 | Phthalonitrile compound |
| CN108431085A (en) * | 2016-01-07 | 2018-08-21 | 株式会社Lg化学 | O-phthalonitrile resin |
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| CN102659628A (en) * | 2012-04-26 | 2012-09-12 | 四川大学 | Phthalonitrile monomer containing aromatic polyamide, synthetizing method thereof and poly phthalonitrile resin produced through solidification of phthalonitrile monomer |
| CN107810177A (en) * | 2015-05-22 | 2018-03-16 | 株式会社Lg化学 | Phthalonitrile compound |
| CN108290830A (en) * | 2015-12-02 | 2018-07-17 | 株式会社Lg化学 | Phthalonitrile compound |
| CN108431085A (en) * | 2016-01-07 | 2018-08-21 | 株式会社Lg化学 | O-phthalonitrile resin |
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