CN106939080B - Nitrile-based resin mixture and preparation method thereof - Google Patents
Nitrile-based resin mixture and preparation method thereof Download PDFInfo
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- CN106939080B CN106939080B CN201610001016.3A CN201610001016A CN106939080B CN 106939080 B CN106939080 B CN 106939080B CN 201610001016 A CN201610001016 A CN 201610001016A CN 106939080 B CN106939080 B CN 106939080B
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
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Abstract
The invention discloses a nitrile resin mixture and a preparation method thereof. The nitrile resin mixture is mainly prepared by taking amino phthalonitrile derivatives and hydroxyl phthalonitrile derivatives as raw materials. The preparation method comprises the steps of dissolving the amino phthalonitrile derivative and the hydroxyl phthalonitrile derivative in a solvent, and drying to obtain a nitrile resin mixture. The nitrile resin mixture has the advantages of low melting point, low viscosity, high reactivity, high heat resistance and excellent mechanical property, and the preparation method is simple and convenient and has low cost.
Description
Technical Field
The invention belongs to the field of polymer composite materials, relates to a nitrile resin mixture and a preparation method thereof, and particularly relates to a phthalonitrile resin mixture and a preparation method thereof.
Background
The fields of aerospace, national defense, military and the like put forward new requirements on the composite material with high temperature resistance, high performance and good flame retardance. Phthalonitrile resins are favored because their cured products have good thermal stability and mechanical properties, as well as excellent thermal oxygen stability, flame retardancy and good moisture resistance. At present, the resin is widely applied to the fields of aerospace, ships, microelectronics, mechanical manufacturing and the like. Typical phthalonitrile resins at present mainly include biphenyl type phthalonitrile resins, bisphenol a type phthalonitrile resins, and aromatic ether type phthalonitrile resins. However, the resin monomers have high melting point, high heat curing temperature and slow reaction, and the obvious gelation phenomenon can be observed only after the resin monomers are treated at 280 ℃ for nearly hundred hours. Their high processing temperature, low curing rate, etc. are the main reasons for poor processability of the resins.
The liquid phase forming method is widely applied due to low cost and excellent mechanical property of the prepared composite material. The key to realizing liquid phase molding of the phthalonitrile resin is to reduce the melting point and viscosity of the resin, and the resin can flow and impregnate fibers only if the melting point and viscosity are reduced. In order to realize liquid phase molding of phthalonitrile resins, researchers have conducted a great deal of research work over the past 20 years. For example, in order to reduce the melting point, Keller group of the American naval laboratory synthesizes asymmetric aromatic ether type phthalonitrile resin monomers with different molecular weights, the melting point is 40-41 ℃, but the viscosity of the resin can be reduced to 1 Pa.s when the temperature is increased to 150 ℃, but the requirement that the liquid phase forming is less than 0.8 Pa.s cannot be met. Li Zheng et al synthesized silicon-based phthalonitrile derivatives, and the test results showed that the derivatives had low melting points, but were easily hydrolyzed at room temperature, resulting in short shelf life of the resins, and the need for low-temperature storage in liquid nitrogen, strict anhydrous environment during use, and difficult application. Liu Xiiaobo et al, which introduces benzoxazine into the main chain of phthalonitrile, synthesized a novel low-melting phthalonitrile derivative, the literature data showed that the melting point was 56-79 ℃, but the viscosity was maintained at 1-6 pas in the temperature range of 80-180 ℃, could not be reduced to 0.8 pas, and the temperature resistance was greatly compromised. Therefore, there is a great deal of research and development work to realize liquid-phase molding of nitrile-based resins.
The concept of eutectic was first proposed in 1999 by Abbott, university of Leicester, UK, which means that in some binary systems, the two components melt into one liquid phase in a proper ratio during the temperature rise. If the two components are mixed in the proper ratio, the two solid components can be melted simultaneously at a temperature that is generally lower than the temperature of each of the pure components, which is called the eutectic temperature, and the mixture is called the eutectic. In a typical case, after 45g of camphor having a melting point of 179 ℃ and 55g of phenyl salicylate having a melting point of 42 ℃ were mixed, the melting point was measured to be only 6 ℃. Related researches show that many physical properties and chemical properties of the eutectic are similar to those of the ionic liquid, so that the eutectic is classified as a novel ionic liquid. At present, eutectic mixtures are widely applied in the fields of organic synthesis, separation engineering, nano material preparation and the like, but application research in preparation of composite material resin matrixes is not reported.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a nitrile resin mixture with low melting point, low viscosity, high reactivity, high heat resistance and excellent mechanical properties and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the nitrile resin mixture is mainly prepared from amino phthalonitrile derivatives and hydroxyl phthalonitrile derivatives.
In the above nitrile resin mixture, preferably, the amino-type phthalonitrile derivative is 70 to 30 parts by mass, and the hydroxyl-type phthalonitrile derivative is 30 to 70 parts by mass.
In the above nitrile resin mixture, preferably, the amino-type phthalonitrile derivative includes one or more of 4- (4-aminophenoxy) phthalonitrile, 4- (3-aminophenoxy) phthalonitrile, 4- (2-aminophenoxy) phthalonitrile, 3- (4-aminophenoxy) phthalonitrile, 3- (3-aminophenoxy) phthalonitrile and 3- (2-aminophenoxy) phthalonitrile.
In the above nitrile resin mixture, preferably, the hydroxy-type phthalonitrile derivative includes one or more of 4- (4-hydroxyphenoxy) phthalonitrile, 4- (3-hydroxyphenoxy) phthalonitrile, 4- (2-hydroxyphenoxy) phthalonitrile, 3- (4-hydroxyphenoxy) phthalonitrile, 3- (3-hydroxyphenoxy) phthalonitrile and 3- (2-hydroxyphenoxy) phthalonitrile.
As a general inventive concept, the present invention also provides a preparation method of a nitrile resin mixture, the preparation method including the steps of: dissolving the amino phthalonitrile derivative and the hydroxyl phthalonitrile derivative in a solvent, and drying to obtain a nitrile resin mixture.
In the above preparation method of the nitrile resin mixture, preferably, the amino type phthalonitrile derivative is 70 to 30 parts by mass, the hydroxyl type phthalonitrile derivative is 30 to 70 parts by mass, and the solvent is 200 to 400 parts by mass.
In the above method for preparing a nitrile resin mixture, preferably, the amino-type phthalonitrile derivative includes one or more of 4- (4-aminophenoxy) phthalonitrile, 4- (3-aminophenoxy) phthalonitrile, 4- (2-aminophenoxy) phthalonitrile, 3- (4-aminophenoxy) phthalonitrile, 3- (3-aminophenoxy) phthalonitrile and 3- (2-aminophenoxy) phthalonitrile.
In the above method for preparing a nitrile resin mixture, preferably, the hydroxy-type phthalonitrile derivative includes one or more of 4- (4-hydroxyphenoxy) phthalonitrile, 4- (3-hydroxyphenoxy) phthalonitrile, 4- (2-hydroxyphenoxy) phthalonitrile, 3- (4-hydroxyphenoxy) phthalonitrile, 3- (3-hydroxyphenoxy) phthalonitrile and 3- (2-hydroxyphenoxy) phthalonitrile.
In the above method for preparing a nitrile resin mixture, preferably, the solvent includes one or more of ethyl acetate, acetone, N-dimethylformamide, dichloromethane and ethanol.
In the above method for preparing a nitrile resin mixture, preferably, the drying temperature is 50 ℃ to 80 ℃, and the drying time is 12 hours to 48 hours.
In the above technical solutions of the present invention, the listed preferred amino-type phthalonitrile derivatives and hydroxyl-type phthalonitrile derivatives can be prepared by conventional methods or obtained commercially.
The innovation points of the invention are as follows:
based on the principle of eutectic, a novel eutectic nitrile-based resin is prepared, the eutectic is expanded from a mixture of organic salt to a mixture of organic amine and phenol, and the preparation method of the eutectic is expanded from a common water solvent evaporation method to an organic solvent evaporation method.
Compared with the prior art, the invention has the advantages that:
1. the nitrile resin mixture is a novel eutectic resin mixture, the eutectic is formed by combining a hydrogen bond donor and a hydrogen bond acceptor with a certain stoichiometric ratio, two groups of phthalonitrile derivatives respectively containing amino and hydroxyl are selected, the molecular weights of the phthalonitrile derivatives are respectively 235 and 236, the melt viscosity of the phthalonitrile derivatives can reach 0.01 Pa.s at the lowest and is far lower than the upper limit of liquid phase forming of 0.8 Pa.s, and therefore, the eutectic prepared by the derivatives can not only effectively reduce the melting point, but also meet the requirement that the liquid phase forming viscosity is less than 0.8 Pa.s. The novel low-melting-point nitrile resin mixture has the advantages of low melting point, low viscosity, high reactivity, good high-temperature resistance, excellent mechanical property and the like, greatly improves the processing property of nitrile resin, widens the application of the nitrile resin, and provides novel resin with excellent comprehensive performance for preparing high-performance composite materials. Meanwhile, the nitrile resin mixture also has the advantages of long shelf life, no hydrolysis, convenient use and the like.
2. The invention provides a design idea of a novel eutectic nitrile-based resin mixture and a preparation method of the resin mixture. The preparation method disclosed by the invention is simple to operate, is suitable for low-cost industrial production, can be widely applied to the fields of coatings, electronic packaging materials, aerospace, microelectronics, mechanical manufacturing, ships, resin-based composite materials and the like, and has a wide market prospect.
Drawings
FIG. 1 is a DSC of a nitrile resin mixture prepared in example 1 of the present invention.
FIG. 2 is a DSC of a nitrile resin mixture prepared in example 2 of the present invention.
FIG. 3 is a DSC of a nitrile resin mixture prepared in example 3 of the present invention.
FIG. 4 is a DSC of a nitrile resin mixture prepared in example 4 of the present invention.
FIG. 5 is a DSC of a nitrile resin mixture prepared in example 5 of the present invention.
Detailed Description
The following embodiments are provided to fully convey the technical idea of the present invention to those skilled in the art. In addition, unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and descriptions of well-known functions and structures that may unnecessarily obscure the gist of the present invention will be omitted in the following description. The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples may be commercially available.
Example 1:
the nitrile resin mixture is prepared from 60 parts of 4- (4-aminophenoxy) phthalonitrile and 40 parts of 4- (4-hydroxyphenoxy) phthalonitrile. The nitrile resin mixture is a eutectic resin mixture.
A preparation method of the nitrile resin mixture of the embodiment includes the following steps:
weighing 60 parts of 4- (4-aminophenoxy) phthalonitrile, 40 parts of 4- (4-hydroxyphenoxy) phthalonitrile and 300 parts of ethyl acetate, uniformly mixing, fully stirring, dissolving, removing most of solvent by a nitrogen blower, putting into a vacuum drying oven at 60 ℃, keeping the vacuum at-0.1 MPa, and keeping for 24 hours to obtain a eutectic resin mixture, namely a nitrile resin mixture.
The nitrile resin mixture prepared in this example was subjected to melting point testing by DSC. The test results are shown in FIG. 1. It can be seen from the figure that the melting point of the resin mixture is 107.51 ℃ which is significantly lower than the melting point of the component 4- (4-aminophenoxy) phthalonitrile (134.5 ℃) and the melting point of the component 4- (4-hydroxyphenoxy) phthalonitrile (150.5 ℃) and that the resin mixture can be polymerized autocatalytically without the addition of curing agents. The rheological test shows that when the temperature exceeds the melting point, the viscosity of the mixture can be rapidly reduced to less than 0.8Pa s, and liquid phase forming can be realized.
Example 2:
a method for preparing a nitrile resin mixture according to the present invention, which comprises substantially the same steps as in example 1, except that: 50 parts of 4- (4-aminophenoxy) phthalonitrile, 50 parts of 4- (4-hydroxyphenoxy) phthalonitrile and 350 parts of ethyl acetate are weighed. The eutectic mixture of nitrile resin prepared in this example was subjected to melting point test by DSC. The test results are shown in FIG. 2. The melting point of the mixed resin was 106.3 ℃. Is significantly lower than the melting point (134.5 ℃) of the component 4- (4-aminophenoxy) phthalonitrile and the melting point (150.5 ℃) of the component 4- (4-hydroxyphenoxy) phthalonitrile. The rheological test shows that when the temperature exceeds the melting point, the viscosity of the mixture can be rapidly reduced to less than 0.8Pa s, and liquid phase forming can be realized.
Example 3:
a method for preparing a nitrile resin mixture according to the present invention, which comprises substantially the same steps as in example 1, except that: 50 parts of 4- (2-aminophenoxy) phthalonitrile, 50 parts of 4- (2-hydroxyphenoxy) phthalonitrile and 350 parts of ethyl acetate are weighed. The eutectic mixture of nitrile resin prepared in this example was subjected to melting point test by DSC. The test results are shown in FIG. 3. The melting point of the mixed resin is 101.04 ℃. Is significantly lower than the melting point (120.9 ℃) of the component 4- (2-aminophenoxy) phthalonitrile and the melting point (143.6 ℃) of the component 4- (2-hydroxyphenoxy) phthalonitrile. The rheological test shows that when the temperature exceeds the melting point, the viscosity of the mixture can be rapidly reduced to less than 0.8Pa s, and liquid phase forming can be realized.
Example 4:
a method for preparing a nitrile resin mixture according to the present invention, which comprises substantially the same steps as in example 1, except that: 50 parts of 3- (4-aminophenoxy) phthalonitrile, 50 parts of 3- (4-hydroxyphenoxy) phthalonitrile and 350 parts of ethyl acetate are weighed. The eutectic mixture of nitrile resin prepared in this example was subjected to melting point test by DSC. The test results are shown in FIG. 4. The melting point of the mixed resin is 148.22 ℃. Is significantly lower than the melting point (198.5 ℃) of the component 3- (4-aminophenoxy) phthalonitrile and the melting point (174.6 ℃) of the component 3- (4-hydroxyphenoxy) phthalonitrile. The rheological test shows that when the temperature exceeds the melting point, the viscosity of the mixture can be rapidly reduced to less than 0.8Pa s, and liquid phase forming can be realized.
Example 5:
a method for preparing a nitrile resin mixture according to the present invention, which comprises substantially the same steps as in example 1, except that: 50 parts of 3- (2-aminophenoxy) phthalonitrile, 50 parts of 3- (2-hydroxyphenoxy) phthalonitrile and 350 parts of ethyl acetate are weighed. The eutectic mixture of nitrile resin prepared in this example was subjected to melting point test by DSC. The test results are shown in FIG. 5. The melting point of the mixed resin is 127.85 ℃. Is significantly lower than the melting point (134.5 ℃) of the component 3- (2-aminophenoxy) phthalonitrile and the melting point (182.4 ℃) of the component 3- (2-hydroxyphenoxy) phthalonitrile. The rheological test shows that when the temperature exceeds the melting point, the viscosity of the mixture can be rapidly reduced to less than 0.8Pa s, and liquid phase forming can be realized.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (6)
1. The nitrile resin mixture is characterized by mainly taking an amino phthalonitrile derivative and a hydroxyl phthalonitrile derivative as raw materials to prepare the nitrile resin mixture, wherein the viscosity of the nitrile resin mixture is lower than 0.8 Pa.s, and the melting point of the nitrile resin mixture is lower than the melting points of the amino phthalonitrile derivative and/or the hydroxyl phthalonitrile derivative;
the hydroxyl type phthalonitrile derivative comprises one or more of 4- (4-hydroxyphenoxy) phthalonitrile, 4- (3-hydroxyphenoxy) phthalonitrile, 4- (2-hydroxyphenoxy) phthalonitrile, 3- (4-hydroxyphenoxy) phthalonitrile, 3- (3-hydroxyphenoxy) phthalonitrile and 3- (2-hydroxyphenoxy) phthalonitrile;
the hydroxyl type phthalonitrile derivative comprises one or more of 4- (4-hydroxyphenoxy) phthalonitrile, 4- (3-hydroxyphenoxy) phthalonitrile, 4- (2-hydroxyphenoxy) phthalonitrile, 3- (4-hydroxyphenoxy) phthalonitrile, 3- (3-hydroxyphenoxy) phthalonitrile and 3- (2-hydroxyphenoxy) phthalonitrile.
2. The nitrile resin mixture according to claim 1, wherein the amino-type phthalonitrile derivative is 70 to 30 parts by mass, and the hydroxy-type phthalonitrile derivative is 30 to 70 parts by mass.
3. A preparation method of a nitrile-based resin mixture is characterized by comprising the following steps: dissolving an amino phthalonitrile derivative and a hydroxyl phthalonitrile derivative in a solvent, and drying to obtain a nitrile resin mixture, wherein the viscosity of the nitrile resin mixture is lower than 0.8 Pa.s, and the melting point of the nitrile resin mixture is lower than that of the amino phthalonitrile derivative and/or the hydroxyl phthalonitrile derivative;
the hydroxyl type phthalonitrile derivative comprises one or more of 4- (4-hydroxyphenoxy) phthalonitrile, 4- (3-hydroxyphenoxy) phthalonitrile, 4- (2-hydroxyphenoxy) phthalonitrile, 3- (4-hydroxyphenoxy) phthalonitrile, 3- (3-hydroxyphenoxy) phthalonitrile and 3- (2-hydroxyphenoxy) phthalonitrile;
the hydroxyl type phthalonitrile derivative comprises one or more of 4- (4-hydroxyphenoxy) phthalonitrile, 4- (3-hydroxyphenoxy) phthalonitrile, 4- (2-hydroxyphenoxy) phthalonitrile, 3- (4-hydroxyphenoxy) phthalonitrile, 3- (3-hydroxyphenoxy) phthalonitrile and 3- (2-hydroxyphenoxy) phthalonitrile.
4. The method for producing a nitrile resin mixture according to claim 3, wherein the amino type phthalonitrile derivative is 70 to 30 parts by mass, the hydroxy type phthalonitrile derivative is 30 to 70 parts by mass, and the solvent is 200 to 400 parts by mass.
5. The method for preparing a nitrile resin mixture as defined in claim 3 or 4, wherein the solvent includes one or more of ethyl acetate, acetone, N-dimethylformamide, dichloromethane and ethanol.
6. The method for preparing a nitrile resin mixture as defined in claim 3 or 4, wherein the drying temperature is 50 ℃ to 80 ℃ and the drying time is 12 hours to 48 hours.
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Citations (4)
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|---|---|---|---|---|
| US6590118B1 (en) * | 1999-09-29 | 2003-07-08 | Novo Nordisk A/S | Aromatic compounds |
| CN1944400A (en) * | 2006-09-14 | 2007-04-11 | 电子科技大学 | Double end group ortho-benzene dimethyl nitrile-benzo oxazine resin, solidified substance and its preparing method and use |
| CN101143928A (en) * | 2007-09-12 | 2008-03-19 | 四川大学 | Poly-o-phthalonitrile resin and its preparing process |
| CN103193977A (en) * | 2013-04-01 | 2013-07-10 | 河北工业大学 | Method for curing poly benzonitrile resin by amino phenoxy phthalonitrile |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6590118B1 (en) * | 1999-09-29 | 2003-07-08 | Novo Nordisk A/S | Aromatic compounds |
| CN1944400A (en) * | 2006-09-14 | 2007-04-11 | 电子科技大学 | Double end group ortho-benzene dimethyl nitrile-benzo oxazine resin, solidified substance and its preparing method and use |
| CN101143928A (en) * | 2007-09-12 | 2008-03-19 | 四川大学 | Poly-o-phthalonitrile resin and its preparing process |
| CN103193977A (en) * | 2013-04-01 | 2013-07-10 | 河北工业大学 | Method for curing poly benzonitrile resin by amino phenoxy phthalonitrile |
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