CN110713597B - Phthalonitrile-based cured material microsphere and preparation method and application thereof - Google Patents
Phthalonitrile-based cured material microsphere and preparation method and application thereof Download PDFInfo
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- CN110713597B CN110713597B CN201810759894.0A CN201810759894A CN110713597B CN 110713597 B CN110713597 B CN 110713597B CN 201810759894 A CN201810759894 A CN 201810759894A CN 110713597 B CN110713597 B CN 110713597B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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Abstract
The invention provides a phthalic anhydrideNitrile-based cured microspheres and a preparation method and application thereof, wherein the method adopts a reaction induced phase separation method to prepare the phthalonitrile-based cured microspheres. The phthalonitrile-based compound is dispersed in the thermoplastic macromolecules in a bead shape, and then the thermoplastic macromolecules are washed away by using a proper organic solvent, so that the high-heat-resistance near-monodisperse solid phthalonitrile-based cured material microspheres can be obtained. The preparation method is simple to operate and easy to control, has the yield close to 100 percent, and is suitable for large-scale industrial production. More importantly, when the phthalonitrile-based cured material microspheres prepared by the method are used for toughening phthalonitrile-based compounds (phthalonitrile compounds shown in formula (I) or phthalonitrile oligomers shown in formula (II)), the impact strength of the prepared cured materials is remarkably improved (for example, the impact strength can be from 7 kJ/m)2The maximum is increased to 23kJ/m2) And shows excellent toughening effect.
Description
Technical Field
The invention belongs to the technical field of thermosetting resin materials, and particularly relates to phthalonitrile-based cured material microspheres and a preparation method and application thereof.
Background
The phthalonitrile-based resin is a novel thermosetting resin system, belongs to one of cyano-based resins, and has a monomer molecular structural formula shown in a formula (a), wherein R is an organic group.
The triazine ring and phthalocyanine ring skeleton structure formed in the curing process of the phthalonitrile-based resin endows the phthalonitrile-based cured resin with excellent heat resistance, the long-term use temperature of the phthalonitrile-based cured resin is over 350 ℃, the glass transition temperature of the phthalonitrile-based cured resin is close to 450 ℃, and the 5 percent weight loss temperature of the phthalonitrile-based cured resin is over 500 ℃, so that the phthalonitrile-based cured resin has wide application fields. However, the high crosslinking density of the resin causes great brittleness of the resin, and cannot meet the requirement of high-performance composite materials on toughness, so that the further application of the resin is limited.
The commonly used thermosetting resin toughening modification methods mainly comprise the following steps: rubber modification, epoxy resin modification, thermoplastic macromolecule modification, rigid particle modification, and the like. But the temperature resistance grades of rubber, epoxy resin and thermoplastic macromolecules are all less than 300 ℃, so that the heat resistance of the toughened and modified phthalonitrile-based resin is obviously reduced. The rigid particles are adopted for toughening modification, the problem of uniform dispersion of the rigid particles needs to be solved, and the rigid particles and a resin matrix interface are obvious, so that the toughening effect cannot be achieved at times. Therefore, no ideal toughening modifier for the phthalonitrile-based resin exists at present.
Microsphere toughening is a new toughening method developed in recent years. Bismaleimide microspheres (CN200410040866.1) and epoxy microspheres (CN201510654028.1, cn201210297791.x) were also reported in succession. In 2018, Wu Xiao (Xiao Wu, Xin Yang, Ran Yu, Xiao-Juan Zhuao, Ying Zhuang, Wei Huang. Highly crosshatched and unmom thermoset epoxy: Preparation and toughening study, Polymer,2018,143,145 and 154) reported that epoxy microspheres modified epoxy resin, the resin toughness was increased nearly twice, and an excellent toughening effect was shown. However, because the epoxy microspheres and the bismaleimide microspheres have poor heat resistance, the heat resistance of the phthalonitrile resin can be obviously reduced during toughening, and the toughening effect cannot be achieved due to the decomposition of the microspheres.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide phthalonitrile-based cured material microspheres and a preparation method and application thereof. The phthalonitrile-based cured resin microspheres are used for toughening phthalonitrile-based cured resin and ensuring that the impact strength of a cured product of the phthalonitrile-based resin is from 7kJ/m2Increased to 23kJ/m2And shows excellent toughening effect.
The purpose of the invention is realized by the following technical scheme:
a microsphere is a phthalonitrile-based cured microsphere, and the chemical composition of the microsphere is a cured product of phthalonitrile-based compound.
According to an embodiment of the invention, the microspheres are solid microspheres.
According to the embodiment of the invention, the microspheres have uniform particle size, are full in sphere and have good monodispersity.
According to an embodiment of the invention, the microspheres have a particle size in the range of 0.5-25 μm.
According to an embodiment of the invention, the microspheres have a particle size distribution between 5 and 25 μm.
According to an embodiment of the invention, the glass transition temperature of the microspheres is above 400 ℃.
According to an embodiment of the present invention, the phthalonitrile-based compound is one or more of a compound of formula (I) or an oligomer of formula (II):
in the formula (I), R is one of the following groups:
in the formula (II), R1And R2The same or different, each independently selected from-O-, -C1～6Alkylene-; n is1Is an integer of 1 to 5;
R3and R4Are the same or different and are each independently selected from-OH,
-OCH＝CH2、-OCH2CH＝CH2、-OCH2C≡CH；
R5is composed of
According to the embodiment of the present invention, if the phthalonitrile-based compound is a mixture, the component contents of each substance are not particularly limited, and may be in any ratio as long as the preparation of phthalonitrile-based cured microspheres of the present invention can be achieved.
Preferably, R is
Or
Preferably, R1、R2Are the same or different and are each independently selected from the group consisting of-O-and-C1～4Alkylene- (more preferably-CH)2-or-O-). More preferably, R1、R2Same, is selected from-CH2-。
Preferably, R3And R4Are the same or different and are each independently selected from the group consisting of-OH and-OCH2CH＝CH2. More preferably, R3And R4And the same, is selected from-OH.
Preferably, R5Is composed of
According to an embodiment of the present invention, the phthalonitrile-based compound may be a compound represented by formula (III):
according to an embodiment of the present invention, the phthalonitrile-based compound may be an oligomer represented by formula (IV):
wherein n is1Is an integer of 1 to 5.
The invention also provides a preparation method of the phthalonitrile-based cured material microspheres, which comprises the following steps:
(1) dissolving a phthalonitrile-based compound, thermoplastic macromolecules and a catalyst in an organic solvent to obtain a mixed system;
(2) removing the organic solvent in the mixed system in the step (1), pouring and curing to obtain a cured substance;
(3) and (3) removing the thermoplastic macromolecules in the cured product obtained in the step (2) to prepare the phthalonitrile-based cured product microspheres.
According to an embodiment of the present invention, the phthalonitrile-based compound is as defined above.
According to an embodiment of the present invention, in the mixed system of step (1), the mass ratio of the phthalonitrile-based compound, the thermoplastic macromolecule, and the catalyst is 100: (20-60): (2-10) namely 100 parts by mass of the phthalonitrile-based compound, 20-60 parts by mass of the thermoplastic macromolecule and 2-10 parts by mass of the catalyst.
Preferably, in the mixed system in the step (1), the mass ratio of the phthalonitrile-based compound to the thermoplastic macromolecule to the catalyst is 100: (20-60): (2-6), alternatively 100: (20-40): (2-10).
Still preferably, in the mixed system of step (1), the mass ratio of the phthalonitrile-based compound, the thermoplastic macromolecule and the catalyst is 100: (20-40): (2-6).
According to an embodiment of the present invention, in the mixed system of step (1), the mass of the organic solvent is 1 to 5 times, for example, 2 times the sum of the mass of the phthalonitrile-based compound, the thermoplastic macromolecule and the catalyst.
According to an embodiment of the present invention, the dissolution temperature of step (1) is 40-80 ℃.
According to the embodiment of the present invention, the thermoplastic macromolecule in step (1) is one or more of polymethyl methacrylate, polyethylene glycol, polypropylene glycol, polylactic acid, and polypropylene carbonate, preferably, the molecular weight of the thermoplastic macromolecule is 5000-.
According to an embodiment of the present invention, the catalyst in step (1) is one or more of stannous chloride, zinc chloride, p-toluenesulfonic acid, trifluorobenzene sulfonic acid, p-phenylenediamine, aniline, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenyl sulfone, 2 ' -bis (4-hydroxyphenyl) propane and 1, 3-bis (3-aminophenoxy) benzene.
According to an embodiment of the present invention, the organic solvent in step (1) is one or a mixture of acetone, ethanol, n-propanol, n-butanol and ethyl acetate.
According to the embodiment of the present invention, the removing method in the step (2) is a conventional manner known to those skilled in the art for removing the organic solvent in the mixed solution, and may be, for example, a manner of performing the removal of the organic solvent by rotary evaporation at a temperature of 80 to 100 ℃.
According to the embodiment of the present invention, the casting in step (2) is a conventional casting method known to those skilled in the art, and illustratively, the organic solvent-removed mixed system is cast in a mold, or is cast by other means.
According to the embodiment of the invention, the curing in the step (2) is performed for 5-10 hours at the temperature of 170-250 ℃ and then for 1-5 hours at the temperature of 250-300 ℃.
According to an embodiment of the present invention, the removing method described in the step (3) is a conventional manner known to those skilled in the art to remove the thermoplastic macromolecules in the cured product, and may be exemplified by dissolving the thermoplastic macromolecules with acetone at 25 to 40 ℃ and filtering.
According to the embodiment of the present invention, the removal in the step (3) is preferably to wash away the thermoplastic macromolecules contained in the cured product with an organic solvent; the organic solvent is one or a mixture of acetone, ethanol and ethyl acetate.
According to an embodiment of the present invention, the preparation method specifically comprises the steps of:
(1) dissolving 100 parts by mass of a phthalonitrile-based compound, 20-60 parts by mass of a thermoplastic macromolecule and 2-10 parts by mass of a catalyst in an organic solvent at 40-80 ℃, and uniformly mixing;
(2) removing the organic solvent at 25-80 deg.C, and pouring the obtained mixture into a mold; curing the mixture in the mold for 5-7 hours at the temperature of 170-250 ℃ and then curing for 1-5 hours at the temperature of 250-300 ℃ to obtain a cured product;
(3) dissolving thermoplastic macromolecules contained in the cured material by using an organic solvent to obtain the phthalonitrile-based cured material microspheres.
The invention also provides phthalonitrile-based cured material microspheres, which are prepared by the method.
The invention also provides application of the phthalonitrile-based cured resin microspheres in toughening modified phthalonitrile-based cured resin.
The invention also provides a composition which comprises the phthalonitrile-based compound and the phthalonitrile-based cured material microsphere.
According to an embodiment of the present invention, the phthalonitrile-based compound is as defined above.
According to the invention, in the composition, the phthalonitrile-based cured material microspheres account for 0.5-10wt%, preferably 1-5 wt% of the composition.
According to the invention, the composition further comprises an organic solvent, wherein the organic solvent accounts for 500wt% of the composition by weight, and preferably 300 wt% of the composition by weight.
According to the invention, the organic solvent is selected, for example, from one or a mixture of several of acetone, ethanol, ethyl acetate and N, N' -dimethylformamide.
The invention also provides a phthalonitrile-based resin cured product which is prepared by blending and curing the composition.
The invention also provides a preparation method of the phthalonitrile-based resin cured product, which comprises the following steps:
and (2) blending and curing a phthalonitrile-based compound, an optional organic solvent and the phthalonitrile-based cured resin microspheres to prepare the phthalonitrile-based resin cured resin.
The blending according to the present invention is carried out by conventional mixing means known to those skilled in the art, for example, by stirring after mixing.
According to the invention, the curing is performed in the temperature range of 170-250 ℃ for 5-10 hours, and then in the temperature range of 250-315 ℃ for 3-5 hours, such as 170 ℃/1 hour, 200 ℃/1 hour, 250 ℃/5 hour, 315 ℃/3 hour.
The invention has the beneficial effects that:
the invention provides phthalonitrile-based cured material microspheres and a preparation method and application thereof. The reaction induced phase separation method is that before the curing reaction begins, a solvent or thermoplastic macromolecules and thermosetting resin (phthalonitrile-based compound) are in a homogeneous phase state, the molecular weight of the thermosetting resin is gradually increased along with the progress of the curing reaction, the compatibility with the thermoplastic macromolecules is gradually deteriorated, the thermosetting resin is not compatible any more in thermodynamics, phase separation begins to occur, and different phase state structures are formed. When the mass ratio of the phthalonitrile-based compound to the thermoplastic macromolecule is 100: (20-60), dispersing the phthalonitrile-based compound in the thermoplastic macromolecules in a bead shape, and then washing off the thermoplastic macromolecules by using a proper organic solvent to obtain the high-heat-resistance near-monodisperse solid phthalonitrile-based cured material microspheres. The preparation method is simple to operate and easy to control, has the yield close to 100 percent, and is suitable for large-scale industrial production. More importantly, when the phthalonitrile-based cured material microspheres prepared by the method are used for toughening phthalonitrile-based compounds (phthalonitrile compounds shown in formula (I) or phthalonitrile oligomers shown in formula (II)), the impact strength of the prepared cured materials is remarkably improved (for example, the impact strength can be from 7 kJ/m)2The maximum is increased to 23kJ/m2) And shows excellent toughening effect.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of phthalonitrile-based cured microspheres prepared in example 1 of the present invention;
FIG. 2 is a laser particle size distribution diagram of phthalonitrile-based cured microspheres prepared in example 1 of the present invention;
FIG. 3 is a DSC of phthalonitrile-based cured microspheres prepared in example 1 of the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) image of the cross section of phthalonitrile-based resin cured material (a casting) toughened by phthalonitrile-based cured material microspheres prepared in example 1 of the present invention.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
In the embodiment, the phthalonitrile-based cured material microsphere is synthesized by the following steps:
(1) in a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 50g of m-phenylene ether type phthalonitrile represented by the formula (III), 10g of polyethylene glycol and 2g of 4, 4' -diaminodiphenylmethane were charged, and then 100g of ethanol was added, heated to 60 ℃, stirred for 30 minutes and mixed uniformly.
(2) After removal of the solvent by rotary evaporation at 60 ℃ using a rotary evaporator, the phthalonitrile mixture is poured into a mold.
(3) And (3) placing the mold in a vacuum drying oven at 160 ℃ and pumping for 5-10 minutes. Until the system is bubble-free, it becomes a homogeneous fluid. Then the mixture is placed in an electric heating constant temperature drying oven for segmented curing to obtain a cured product, and the curing and temperature rising process is as follows: 170 ℃/1h, 200 ℃/1h, 250 ℃/5h and 280 ℃/3 h.
(4) Taking out the cured product in the mold, smashing, pouring into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser tube, adding 100g of ethanol, heating to 60 ℃, stirring to dissolve thermoplastic macromolecules, repeatedly washing for 3 times, and filtering to obtain the phthalonitrile-based cured product microspheres.
Referring to fig. 1, it is an SEM photograph of the phthalonitrile-based cured microspheres prepared in this example. It can be seen that the microspheres have uniform particle size, are spherical and full, and have good monodispersity.
Referring to fig. 2, it is a laser particle size analysis diagram of the phthalonitrile-based cured microspheres prepared in this example. It can be seen that the particle size distribution of the microspheres is narrow, mainly concentrated at 10 μm, consistent with SEM results.
Referring to FIG. 3, it is a DSC chart of phthalonitrile-based cured microspheres prepared in this example. It can be seen that the microspheres have no significant glass transition at 400 ℃ and are excellent in heat resistance.
Example 2
(1) In a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 50g of m-phenylene ether type phthalonitrile represented by the formula (III), 15g of polymethyl methacrylate and 2g of 4, 4' -diaminodiphenyl sulfone were charged, and then 100g of ethanol was added, heated to 60 ℃, stirred for 30 minutes and mixed uniformly.
(2) After removal of the solvent by rotary evaporation at 60 ℃ using a rotary evaporator, the phthalonitrile mixture is poured into a mold.
(3) And (3) placing the mold in a vacuum drying oven at 160 ℃ and pumping for 5-10 minutes. Until the system is bubble-free, it becomes a homogeneous fluid. Then the mixture is placed in an electric heating constant temperature drying oven for segmented curing to obtain a cured product, and the curing and temperature rising process is as follows: 170 ℃/1h, 200 ℃/1h, 250 ℃/5h and 280 ℃/3 h.
(4) Taking out the cured product in the mold, smashing, pouring into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser tube, adding 100g of ethanol, heating to 60 ℃, stirring to dissolve thermoplastic macromolecules, repeatedly washing for 3 times, and filtering to obtain the phthalonitrile-based cured product microspheres.
Example 3
(1) In a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser were charged 50g of m-phenylene ether type phthalonitrile represented by the formula (III), 15g of polymethyl methacrylate and 3g of p-toluenesulfonic acid, followed by addition of 100g of ethanol, heating to 40 ℃, stirring for 30 minutes and mixing well.
(2) After removal of the solvent by rotary evaporation at 60 ℃ using a rotary evaporator, the phthalonitrile mixture is poured into a mold.
(3) And (3) placing the mold in a vacuum drying oven at 160 ℃ and pumping for 5-10 minutes. Until the system is bubble-free, it becomes a homogeneous fluid. Then the mixture is placed in an electric heating constant temperature drying oven for segmented curing to obtain a cured product, and the curing and temperature rising process is as follows: 170 ℃/1h, 200 ℃/1h, 250 ℃/5h and 280 ℃/3 h.
(4) Taking out the cured product in the mold, smashing, pouring into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser tube, adding 100g of ethanol, heating to 60 ℃, stirring to dissolve thermoplastic macromolecules, repeatedly washing for 3 times, and filtering to obtain the phthalonitrile-based cured product microspheres.
Example 4
(1) In a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 50g of the oligomer represented by the formula (IV), 10g of polyethylene glycol and 2g of p-toluenesulfonic acid were charged, and then 100g of acetone was added, heated to 40 ℃ and stirred for 30 minutes, followed by uniform mixing.
(2) After the solvent was removed by rotation at 25 ℃ at room temperature using a rotary evaporator, the phthalonitrile mixture was poured into a mold.
(3) And (3) placing the die in a vacuum drying oven at 140 ℃ for pumping for 5-10 minutes. Until the system is bubble-free, it becomes a homogeneous fluid. Then the mixture is placed in an electric heating constant temperature drying oven for segmented curing to obtain a cured product, and the curing and temperature rising process is as follows: 170 ℃/1h, 200 ℃/1h, 250 ℃/3h and 280 ℃/2 h.
(4) Taking out the cured product in the mold, smashing, pouring into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser tube, adding 100g of acetone, heating to 40 ℃, stirring to dissolve thermoplastic macromolecules, repeatedly washing for 3 times, and filtering to obtain the phthalonitrile-based cured product microspheres.
Example 5
(1) In a three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 50g of the oligomer represented by the formula (IV), 15g of polyethylene glycol and 2g of diaminodiphenyl sulfone were charged, and then 100g of acetone was added, heated to 40 ℃ and stirred for 30 minutes, followed by uniform mixing.
(2) After the solvent was removed by rotation at 25 ℃ at room temperature using a rotary evaporator, the phthalonitrile mixture was poured into a mold.
(3) And (3) placing the die in a vacuum drying oven at 140 ℃ for pumping for 5-10 minutes. Until the system is bubble-free, it becomes a homogeneous fluid. Then the mixture is placed in an electric heating constant temperature drying oven for segmented curing to obtain a cured product, and the curing and temperature rising process is as follows: 170 ℃/1h, 200 ℃/1h, 250 ℃/3h and 280 ℃/2 h.
(4) Taking out the cured product in the mold, smashing, pouring into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser tube, adding 100g of acetone, heating to 40 ℃, stirring to dissolve thermoplastic macromolecules, repeatedly washing for 3 times, and filtering to obtain the phthalonitrile-based cured product microspheres.
Example 6
The phthalonitrile-based cured microspheres prepared in examples 1 to 5 were added to phthalonitrile oligomer represented by formula (IV) in an amount of 1%, and the two were stirred at 120 ℃ for 30min, mixed uniformly, and poured into a mold. And (3) placing the mold in a vacuum drying oven at 150 ℃ for pumping for 5-10 minutes. Until the system is bubble-free, it becomes a homogeneous fluid. Then the mixture is placed in an electric heating constant temperature drying oven for segmented curing. The curing and temperature rising process comprises the following steps: 170 ℃/1h, 200 ℃/1h, 250 ℃/5h, 315 ℃/3 h. Obtaining the microsphere toughened phthalonitrile-based resin cured product.
See table 1, which is the impact strength of the phthalonitrile based resin cured material (specifically, phthalonitrile oligomer cured resin shown in formula (IV)) toughened by phthalonitrile based cured material microspheres prepared in examples 1 to 5, and is specifically a parallel experiment for 5 times. It can be seen that the impact strength of the cured resin is from 7 kJ-m2The maximum is increased to 23kJ/m2And shows excellent toughening effect.
Referring to FIG. 4, it is an SEM image of the impact cross section of a phthalonitrile-based resin cured material (a casting) toughened by phthalonitrile-based cured material microspheres prepared in example 1. It can be seen that after the cracks pass through the microspheres, the cracks are obviously expanded and dispersed, which shows that the microspheres can well absorb energy and play a toughening role.
TABLE 1 impact Strength of toughened phthalonitrile-based resin cured product prepared in inventive example 6
As can be seen from the data in Table 1, the phthalonitrile-based microsphere toughened phthalonitrile oligomer of formula (IV) prepared by using phthalonitrile-based microspheres of different molecular structures has toughening effect, and particularly the microsphere toughened phthalonitrile oligomer of formula (IV) prepared by using formula (III) has obvious toughening effect.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (32)
1. A microsphere is a phthalonitrile-based cured microsphere and is characterized in that the microsphere is a cured product of a phthalonitrile-based compound and is a solid microsphere;
the phthalonitrile-based compound is one or more of a compound shown in a formula (I) or an oligomer shown in a formula (II):
formula (I)
Formula (II)
In the formula (I), R is one of the following groups:
in the formula (II), R1And R2The same or different, each independently selected from-O-, -C1~6Alkylene-; n is1Is an integer of 1 to 5;
R3and R4Are the same or different and are each independently selected from-OH,
、-OCH=CH2、-OCH2CH=CH2、-OCH2C≡CH；
R5is composed of
。
2. The microspheres of claim 1, wherein the microspheres have a particle size in the range of 0.5-25 μm.
3. The microspheres of claim 1, wherein the microspheres have a particle size distribution of between 5 and 25 μm.
4. The microsphere of claim 1, wherein the glass transition temperature of the microsphere is above 400 ℃.
5. The microsphere of claim 1, wherein R is
Or
。
6. The microsphere of claim 1, wherein R is1、R2Are the same or different and are each independently selected from the group consisting of-O-and-C1~4Alkylene-.
7. The microsphere of claim 6, wherein R is1、R2Same, is selected from-CH2-。
8. The microsphere of claim 1, wherein R is3And R4Are the same or different and are each independently selected from the group consisting of-OH and-OCH2CH=CH2。
9. The microsphere of claim 8, wherein R is3And R4And the same, is selected from-OH.
10. The microsphere of claim 1, wherein the phthalonitrile-based compound is a compound of formula (III):
formula (III).
11. The microsphere of claim 1, wherein the phthalonitrile-based compound is an oligomer of formula (IV):
formula (IV)
Wherein n is1Is an integer of 1 to 5.
12. A method for preparing phthalonitrile-based cured resin microspheres as claimed in claim 1, comprising the steps of:
(1) dissolving a phthalonitrile-based compound, thermoplastic macromolecules and a catalyst in an organic solvent to obtain a mixed system; the thermoplastic macromolecule is one or a mixture of polymethyl methacrylate, polyethylene glycol and polypropylene glycol;
(2) removing the organic solvent in the mixed system in the step (1), pouring and curing to obtain a cured substance;
(3) removing thermoplastic macromolecules in the cured substance obtained in the step (2) to prepare phthalonitrile-based cured substance microspheres;
in the mixed system in the step (1), the mass ratio of the phthalonitrile-based compound to the thermoplastic macromolecule to the catalyst is 100: (20-60): (2-10) namely 100 parts by mass of the phthalonitrile-based compound, 20-60 parts by mass of the thermoplastic macromolecule and 2-10 parts by mass of the catalyst.
13. The production method according to claim 12, wherein in the mixed system of step (1), the mass ratio of the phthalonitrile-based compound, the thermoplastic macromolecule, and the catalyst is 100: (20-60): (2-6).
14. The production method according to claim 13, wherein in the mixed system of step (1), the mass ratio of the phthalonitrile-based compound, the thermoplastic macromolecule, and the catalyst is 100: (20-40): (2-6).
15. The production method according to claim 12, wherein the mass of the organic solvent in the mixed system of the step (1) is 1 to 5 times the sum of the mass of the phthalonitrile-based compound, the thermoplastic macromolecule and the catalyst.
16. The method according to claim 12, wherein the dissolution temperature in the step (1) is 40 to 80 ℃.
17. The method as claimed in claim 12, wherein the molecular weight of the thermoplastic macromolecule is 5000-.
18. The method according to claim 12, wherein the catalyst in step (1) is one or more selected from the group consisting of p-toluenesulfonic acid, trifluorobenzene sulfonic acid, p-phenylenediamine, aniline, 4 '-diaminodiphenylmethane and 4, 4' -diaminodiphenylsulfone.
19. The preparation method according to claim 12, wherein the organic solvent in step (1) is one or more selected from acetone, ethanol, n-propanol, n-butanol, and ethyl acetate.
20. The method as claimed in claim 12, wherein the curing in step (2) is performed at 170-250 ℃ for 5-10 hours and then at 250-300 ℃ for 1-5 hours.
21. The production method according to claim 12, wherein the thermoplastic macromolecules contained in the cured product are washed away with an organic solvent in the step (3); the organic solvent is one or a mixture of acetone, ethanol and ethyl acetate.
22. The method of manufacturing according to claim 12, comprising the steps of:
(1) dissolving 100 parts by mass of a phthalonitrile-based compound, 20-60 parts by mass of a thermoplastic macromolecule and 2-10 parts by mass of a catalyst in an organic solvent at 40-80 ℃, and uniformly mixing; the thermoplastic macromolecule is one or a mixture of polymethyl methacrylate, polyethylene glycol, polypropylene glycol, polylactic acid and polypropylene carbonate;
(2) removing the organic solvent at 25-80 deg.C, and pouring the obtained mixture into a mold; curing the mixture in the mold for 5-7 hours at the temperature of 170-250 ℃ and then curing for 1-5 hours at the temperature of 250-300 ℃ to obtain a cured product;
(3) dissolving thermoplastic macromolecules contained in the cured material by using an organic solvent to obtain the phthalonitrile-based cured material microspheres.
23. A phthalonitrile-based cured microsphere prepared by the method of any one of claims 12 to 22.
24. Use of the phthalonitrile-based cured resin microspheres of any one of claims 1 to 11, 23 for toughening a modified phthalonitrile-based cured resin.
25. A composition comprising a phthalonitrile-based compound and phthalonitrile-based cured resin microspheres as claimed in any one of claims 1 to 11, 23.
26. The composition as claimed in claim 25, wherein the phthalonitrile-based cured microspheres account for 0.5-10wt% of the composition.
27. The composition as claimed in claim 25, further comprising an organic solvent in an amount of 100-500wt% based on the weight of the composition.
28. The composition of claim 27, wherein the organic solvent is selected from the group consisting of acetone, ethanol, ethyl acetate, and N, N' -dimethylformamide.
29. A cured product of a phthalonitrile-based resin, which is prepared by blending and curing the composition according to any one of claims 25 to 28.
30. The method for producing a cured product of a phthalonitrile-based resin according to claim 29, which comprises the steps of:
and (2) blending and curing a phthalonitrile-based compound, an optional organic solvent and phthalonitrile-based cured resin microspheres to prepare the phthalonitrile-based resin cured resin.
31. The method as claimed in claim 30, wherein the curing is performed at 170-250 ℃ for 5-10 hours and then at 250-315 ℃ for 3-5 hours.
32. The method of claim 30, wherein the curing process is: 170 ℃/1h, 200 ℃/1h, 250 ℃/5h, 315 ℃/3 h.
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|---|---|---|---|---|
| CN105566629A (en) * | 2016-03-18 | 2016-05-11 | 中国科学院化学研究所 | Porous phthalonitrile resin and preparation method thereof, and application of resin |
| CN106000466A (en) * | 2016-05-19 | 2016-10-12 | 中北大学 | Immobilized metal phthalocyanines catalyst prepared by aid of synchronous synthesis and immobilization processes and methods for preparing and applying immobilized metal phthalocyanines catalyst |
| KR20170060897A (en) * | 2015-11-25 | 2017-06-02 | 주식회사 엘지화학 | Phthalonitrile compound |
| WO2018101728A1 (en) * | 2016-11-30 | 2018-06-07 | 주식회사 엘지화학 | Curable composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170060897A (en) * | 2015-11-25 | 2017-06-02 | 주식회사 엘지화학 | Phthalonitrile compound |
| CN105566629A (en) * | 2016-03-18 | 2016-05-11 | 中国科学院化学研究所 | Porous phthalonitrile resin and preparation method thereof, and application of resin |
| CN106000466A (en) * | 2016-05-19 | 2016-10-12 | 中北大学 | Immobilized metal phthalocyanines catalyst prepared by aid of synchronous synthesis and immobilization processes and methods for preparing and applying immobilized metal phthalocyanines catalyst |
| WO2018101728A1 (en) * | 2016-11-30 | 2018-06-07 | 주식회사 엘지화학 | Curable composition |
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