CN115650879A - Amino phenoxy phthalonitrile resin, polymer and preparation method thereof - Google Patents
Amino phenoxy phthalonitrile resin, polymer and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of synthesis of high polymer materials, and relates to amino phenoxy phthalonitrile resin, a polymer and a preparation method thereof. The invention not only can solve a series of problems caused by introducing a catalyst/a curing agent and the like in the processing and forming process of the existing phthalonitrile resin, but also simplifies the forming process of the polymer and improves the production efficiency. Meanwhile, the resin synthesis preparation process has low energy consumption, safety and controllability, and the polymer has outstanding electrical property, can provide a new resin type for high-performance materials for electronic information, and is suitable for market popularization and application.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to amino phenoxy phthalonitrile resin, a polymer and a preparation method thereof.
Background
The phthalonitrile resin is an aromatic compound containing a dinitrile group in a molecular structure, and a polymer can be obtained by adopting a thermal polymerization or catalytic polymerization mode, and the polymer has abundant aromatic heterocyclic rings, so that the polymer shows outstanding self-flame retardance, high temperature resistance and excellent structural characteristics. In recent years, the material has attracted much attention in the fields of thermal protection of weaponry, structural materials for aerospace, and light-weight high-strength materials for rail transit.
The resin was originally born by the Keller research team in the U.S. naval laboratories. In the documents of j.macromol.sci. -chem., a18, 931 (1982), etc., the synthesis of biphenyl type and hydroquinone type nitrile monomers, the curing reaction studies and the performance studies of partial applications of organic amine such as crosslinking, acid, metal salt, etc. are mainly reported. J.polym.sci., partA: curing reactions of biphenyl type dinitrile monomers with a series of novel aromatic ether diamines were mainly studied in Polymer. Chem.36, 1885 (1998). The main problems of the resin in the application process are that the phthalonitrile resin has low self-reactivity, and a catalyst or a curing agent with a specific structure is required to initiate and promote the polymerization of the phthalonitrile resin so as to obtain a polymer with outstanding performance. However, the problems of poor compatibility among multiple phases and difficult control of dispersion uniformity exist in the external catalyst and the curing agent, and the problems are more obvious particularly in the case of inorganic catalysts and curing agents.
In addition, because the polymerization reaction of the phthalonitrile resin can be completed only by long-time treatment at a high temperature of more than 280 ℃, most of the organic catalysts and curing agents are difficult to match with the processing technology of phthalonitrile at present, and a large amount of micro defects appear in the phthalonitrile polymer after the formation due to the decomposition/sublimation of the organic catalysts and the curing agents at a high temperature, so that the comprehensive performance of the polymer is damaged; in addition, the existing phthalonitrile resin system has the problems of high energy consumption, high pollution, complex process, difficult regulation and control of polymer performance and the like in the process of processing and forming, and does not meet the trend of energy conservation, emission reduction and green sustainable development advocated at the present stage.
Disclosure of Invention
In view of the above, the present invention has made a great deal of research on phthalonitrile resin, and prepares phthalonitrile resin with autocatalysis characteristic by introducing amino functional groups through molecular structure design synthesis, so as to optimize the polymerization molding process thereof.
It should be noted that, because of the reaction inertness of the existing phthalonitrile resin, it is difficult to form a polymer with reliable performance at a relatively low temperature in a short time, and the method of adding a curing agent, a crosslinking agent, a copolymerization resin system, etc. is usually adopted to initiate the polymerization reaction of phthalonitrile resin, thereby obtaining a polymer with high performance.
The following points can be improved in the specific implementation process:
1) The currently adopted phthalonitrile resin system has a high melting point, and the problems of high energy consumption, high danger, difficult control of prepolymerization degree and the like exist in the process of preparing a prepolymer and a polymer by adopting a melt processing mode;
2) The existing phthalonitrile resin has poor solubility, a strong-polarity high-boiling-point solvent is generally adopted for dissolution processing, and the solvent needs to be removed in the later polymer preparation process, so that on one hand, a large amount of waste of the solvent is caused, and meanwhile, the solvent removal process also brings great pressure to the environment and generates certain potential safety hazard;
3) The curing agent, the cross-linking agent and the like introduced in the prior art have the phenomena of volatilization, sublimation, decomposition and the like in the process of phthalonitrile resin polymerization due to poor heat resistance of the curing agent, the cross-linking agent and the like, so that micro defects appear in a polymer structure to reduce the structural performance of the polymer;
4) The post-curing molding temperature of the prior phthalonitrile resin is high, the requirement on equipment is strict, and simultaneously, the energy consumption is extremely high.
The invention discloses an amino phenoxy phthalonitrile resin and a synthesis method thereof, which can solve a series of problems caused by introducing a catalyst/a curing agent and the like in the processing and forming process of the existing phthalonitrile resin, simplify the forming process of a polymer and improve the production efficiency. Meanwhile, the resin synthesis preparation process has low energy consumption, safety and controllability, and the polymer has outstanding electrical property, and can provide a new resin type for high-performance materials for electronic information.
In order to achieve the above purpose, the invention provides the following technical scheme:
an amino phenoxy phthalonitrile resin, the structure of which is shown in formula 1:
and, the synthesis method of the aminophenoxy phthalonitrile resin comprises the following steps:
1) Adding m-aminophenol, 4-nitrophthalonitrile, potassium carbonate and N, N-dimethylformamide into a three-necked bottle in proportion, and stirring and mixing at room temperature to obtain a mixed solution for later use;
2) Slowly heating the mixed solution to 60-80 ℃, and keeping stirring for continuous reaction for 5-8 hours to obtain a reaction solution;
3) After the reaction system is naturally cooled to below 50 ℃, transferring the reaction liquid into sufficient deionized water, and precipitating to separate out a product;
4) Filtering and separating the precipitated product, then repeatedly washing and filtering by adopting heated deionized water at the temperature of 80-90 ℃, and finishing washing when the conductivity of the filtrate is detected to be lower than 30 us/cm;
5) Drying the product filtered in the step 4), setting the temperature to be 90-110 ℃, and drying for 8-12 hours to obtain the aminophenoxy phthalonitrile resin.
Optionally, in step 1), the molar ratio of the m-aminophenol, the 4-nitrophthalonitrile and the potassium carbonate is 1.01, and feeding deviation from the ratio results in increase of synthesis side reaction and low product purity, wherein when the addition amount of the potassium carbonate is higher, the difficulty of washing and purifying the synthesis product is increased sharply, and when the addition amount of the potassium carbonate is lower than the ratio, the reaction efficiency is reduced, and the product yield is low within a specified time.
And the weight ratio of the sum of the weight of the m-aminophenol, the 4-nitrophthalonitrile and the potassium carbonate to the weight of the N, N-dimethylformamide is 1: (0.8-1.2), above which the viscosity of the reaction system is high, and the reactants are not mixed sufficiently, resulting in incomplete reaction; when the ratio is lower than the above range, on the one hand, the solvent is wasted, the difficulty in separation and purification of subsequent products is increased, and on the other hand, the reaction rate is reduced, resulting in a reduction in yield.
Optionally, the slow heating rate in the step 2) is 5-10 ℃/min; the temperature rise rate is higher than the above rate, so that the danger of explosive boiling and the like caused by the accumulation of the heat efficiency of the reaction system is easily caused, and the production efficiency is low due to the rate lower than the above rate; the reaction temperature is set to be 60-80 ℃, and when the reaction temperature is higher than the temperature, the side reaction is increased rapidly, so that the product yield is low, the impurity content is high, and when the reaction temperature is lower than the temperature, the reaction rate is slow, and the production efficiency is reduced; the reaction time is set to be 5-8 hours, and the longer the reaction time is, energy is wasted, the production efficiency is low, the reaction is insufficient and the product yield is low.
In the step 3), the weight of the added deionized water is 4-6 times of that of the N, N-dimethylformamide; above this ratio, water resources are wasted and the burden of wastewater treatment is increased; below this ratio, the product cannot be precipitated sufficiently, resulting in product agglomeration, solvent-coated impurities inside, and increased difficulty in subsequent purification.
In addition, the invention adopts the heated deionized water with the temperature of 80-90 ℃ for repeated washing and filtration, the energy consumption is high when the temperature is higher than the temperature, the operation is inconvenient, the solubility to impurities is reduced when the temperature is lower than the temperature, and the purification effect is not good; when the conductivity of the filtrate is detected to be higher than a set value, the content of impurities exceeds the standard and does not meet the electrical property application requirements of subsequent polymers; below this set value, the purification difficulty is greater, resulting in water waste and increased difficulty in wastewater treatment.
Optionally, the drying temperature is set to be 90-110 ℃, the drying time is set to be 8-12 hours, when the temperature is higher than the temperature, the energy consumption is increased, the property transformation in the product drying process is caused, and the drying efficiency is low when the temperature is lower than the temperature; longer than this time results in wasted energy and shorter than this time the drying is insufficient.
In addition, the present invention also claims a method for preparing an aminophenoxy phthalonitrile polymer, comprising the steps of:
(A) Coating the synthesized amino phenoxy phthalonitrile resin on a quartz glass slide, and placing the quartz glass slide in a drying oven for pretreatment for 10 to 20 minutes at 130 to 150 ℃ for later use;
(B) And after the resin is spread on a glass slide, raising the temperature to 200 ℃, and carrying out heat treatment for 2-4 hours to obtain the aminophenoxy phthalonitrile polymer.
It is worth to state that, the pretreatment of 130-150 ℃ for 10-20 minutes in the step A) is to make the resin sample spread evenly on the glass slide, and above the temperature, the resin starts to generate polymerization reaction and is difficult to control, and below the temperature, the resin melt viscosity is poor, and the spreading effect is poor; pretreatment longer than this time reduces efficiency, and shorter than this time, the resin sample does not spread sufficiently, affecting the physical dimensions of the subsequent polymer sample.
The temperature in the step B) is set to be 200 ℃, the temperature is higher than the temperature, the energy consumption is increased, the reaction is too violent, the full polymerization of active groups is not facilitated, the internal crosslinking degree of the polymer is low, the performance of the polymer is poor, the reaction activity is low, the polymerization is insufficient, and the performance of the polymer is poor when the temperature is lower than the temperature; the heat treatment time is 2-4 hours, the time is longer than that, the energy consumption is increased, the efficiency is reduced, and the time is shorter than that, the polymerization is insufficient, and the polymer performance is uncontrollable.
In addition, the temperature and time of the heat treatment are chosen to ensure sufficient polymerization of the resin system, above which there is a tendency to waste resources and to reduce the production efficiency, and below which there is no possibility of complete polymerization, resulting in a reduction in the structural strength and thermal stability of the polymer.
According to the technical scheme, compared with the prior art, the amino phenoxy phthalonitrile resin, the polymer and the preparation method thereof provided by the invention have the following excellent effects:
1) The phthalonitrile resin with the autocatalytic polymerization characteristic can be obtained through simple and mild process conditions, so that the production process and flow are simplified;
2) The phase splitting problem and the resource waste problem caused by the addition of a catalyst/a curing agent in a resin system and high-temperature molding are improved by utilizing the structure and the polymerization reaction characteristic of a resin matrix;
3) Obviously reduces the processing and forming temperature of the phthalonitrile resin, obtains a polymer material with excellent thermal stability and functional characteristics, simplifies the processing technology and reduces the production cost.
In conclusion, the process method provided by the invention is simple and convenient to operate, high in efficiency, low in energy consumption, green and environment-friendly, and suitable for popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows the relative dielectric constants of the samples obtained in the examples and comparative examples.
FIG. 2 shows the relative dielectric loss of the samples obtained in the examples and comparative examples.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings of the specification, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The embodiment of the invention discloses amino phenoxy phthalonitrile resin, a polymer and a preparation method thereof.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1
A synthetic method of amino phenoxy phthalonitrile resin comprises the following steps:
a) Adding 10.91g of m-aminophenol, 17.3g of 4-nitrophthalonitrile, 13.94g of potassium carbonate and 33.7g of N, N-dimethylformamide into a three-necked bottle, and stirring and mixing uniformly at room temperature;
b) Slowly heating to the set temperature of 60 ℃, and keeping stirring for continuous reaction for 6 hours;
c) After the reaction system is naturally cooled to below 50 ℃, transferring the reaction liquid to 135g of deionized water, and precipitating to separate out a product;
d) Filtering and separating the precipitated product, repeatedly washing and filtering by adopting heated deionized water at 80 ℃, and finishing washing when the conductivity of the filtrate is detected to be 30 us/cm;
e) And (3) drying the filtered product in a drying oven at the set temperature of 100 ℃ for 8 hours to obtain the aminophenoxy phthalonitrile resin.
And, a method for preparing an aminophenoxy phthalonitrile polymer, comprising the steps of:
a) Coating the amino phenoxy phthalonitrile resin on a quartz glass slide, and placing the quartz glass slide in a drying oven for pretreatment for 15 minutes at 130 ℃;
b) And after the sample is spread on a glass slide, raising the temperature to 200 ℃, and carrying out heat treatment for 2 hours to prepare the aminophenoxy phthalonitrile polymer.
Example 2
A synthetic method of amino phenoxy phthalonitrile resin comprises the following steps:
a) Adding 10.91g of m-aminophenol, 17.3g of 4-nitrophthalonitrile, 13.94g of potassium carbonate and 50.6g of N, N-dimethylformamide into a three-necked bottle, and stirring and mixing uniformly at room temperature;
b) Slowly heating to the set temperature of 65 ℃, and keeping stirring for continuous reaction for 6 hours;
c) After the reaction system is naturally cooled to below 50 ℃, transferring the reaction liquid to 150g of deionized water, and precipitating to separate out a product;
d) Filtering and separating the precipitated product, repeatedly washing and filtering by using heated deionized water at 85 ℃, and finishing washing when the conductivity of the filtrate is detected to be 29 us/cm;
e) And (3) drying the filtered product in a drying oven at the set temperature of 110 ℃ for 8 hours to obtain the aminophenoxy phthalonitrile resin.
And, a method for preparing an aminophenoxy phthalonitrile polymer, comprising the steps of:
a) Coating the amino phenoxy phthalonitrile resin on a quartz glass slide, and placing the quartz glass slide in a drying oven for pretreatment for 10 minutes at 140 ℃;
b) And after the sample is spread on a glass slide, raising the temperature to 200 ℃, and carrying out heat treatment for 4 hours to prepare the aminophenoxy phthalonitrile polymer.
Example 3
A synthetic method of amino phenoxy phthalonitrile resin comprises the following steps:
a) Adding 10.91g of m-aminophenol, 17.3g of 4-nitrophthalonitrile, 13.94g of potassium carbonate and 35g of N, N-dimethylformamide into a three-necked bottle, and stirring and mixing uniformly at room temperature;
b) Slowly heating to the set temperature of 70 ℃, and keeping stirring for continuous reaction for 5 hours;
c) After the reaction system is naturally cooled to below 50 ℃, transferring the reaction liquid into 140g of deionized water, and precipitating to separate out a product;
d) Filtering and separating the precipitated product, repeatedly washing and filtering by using heated deionized water at 85 ℃, and finishing washing when the conductivity of the filtrate is detected to be 30 us/cm;
e) And (3) drying the filtered product in a drying oven at the set temperature of 100 ℃ for 12 hours to obtain the aminophenoxy phthalonitrile resin.
And, a method for preparing an aminophenoxy phthalonitrile polymer, comprising the steps of:
a) Coating the amino phenoxy phthalonitrile resin on a quartz glass slide, and placing the quartz glass slide in a drying oven for pretreatment for 10 minutes at 150 ℃;
b) And after the sample is spread on a glass slide, raising the temperature to 200 ℃, and carrying out heat treatment for 3 hours to prepare the aminophenoxy phthalonitrile polymer.
Example 4
A synthetic method of amino phenoxy phthalonitrile resin comprises the following steps:
a) Adding 10.91g of m-aminophenol, 17.3g of 4-nitrophthalonitrile, 13.94g of potassium carbonate and 35gN, N-dimethylformamide into a three-necked bottle, and stirring and mixing uniformly at room temperature;
b) Slowly heating to the set temperature of 80 ℃, and keeping stirring for continuous reaction for 5 hours;
c) After the reaction system is naturally cooled to below 50 ℃, transferring the reaction liquid to 150g of deionized water, and precipitating to separate out a product;
d) Filtering and separating the precipitated product, repeatedly washing and filtering by adopting heated deionized water at 90 ℃, and finishing washing when the conductivity of the filtrate is detected to be 30 us/cm;
e) And (3) drying the filtered product in a drying oven at the set temperature of 100 ℃ for 12 hours to obtain the aminophenoxy phthalonitrile resin.
And, a method for preparing an aminophenoxy phthalonitrile polymer, comprising the steps of:
a) Coating the amino phenoxy phthalonitrile resin on a quartz glass slide, and placing the quartz glass slide in a drying oven for pretreatment for 10 minutes at 140 ℃;
b) And after the sample is spread on a glass slide, raising the temperature to 200 ℃, and carrying out heat treatment for 3 hours to prepare the aminophenoxy phthalonitrile polymer.
Example 5
A synthetic method of amino phenoxy phthalonitrile resin comprises the following steps:
a) Adding 10.91g of m-aminophenol, 17.3g of 4-nitrophthalonitrile, 13.94g of potassium carbonate and 40g of N, N-dimethylformamide into a three-necked bottle, and stirring and mixing uniformly at room temperature;
b) Slowly heating to 75 ℃, and keeping stirring for continuous reaction for 8 hours;
c) After the reaction system is naturally cooled to below 50 ℃, transferring the reaction liquid to 150g of deionized water, and precipitating to separate out a product;
d) Filtering and separating the precipitated product, repeatedly washing and filtering by adopting heated deionized water at 90 ℃, and finishing washing when the conductivity of the filtrate is detected to be 30 us/cm;
e) And (3) drying the filtered product in a drying oven at the set temperature of 100 ℃ for 12 hours to obtain the aminophenoxy phthalonitrile resin.
And, a method for preparing an aminophenoxy phthalonitrile polymer, comprising the steps of:
a) Coating the amino phenoxy phthalonitrile resin on a quartz glass slide, and placing the quartz glass slide in a drying oven for pretreatment for 15 minutes at 135 ℃;
b) And after the sample is spread on a glass slide, raising the temperature to 200 ℃, and carrying out heat treatment for 3 hours to prepare the aminophenoxy phthalonitrile polymer.
Comparative example 1
A synthetic method of amino phenoxy phthalonitrile resin comprises the following steps:
a) Adding 10.91g of m-aminophenol, 17.3g of 4-nitrophthalonitrile, 12.00g of potassium carbonate and 35g of N, N-dimethylformamide into a three-necked bottle, and stirring and mixing uniformly at room temperature;
b) Slowly heating to the set temperature of 70 ℃, and keeping stirring for continuous reaction for 6 hours;
c) After the reaction system is naturally cooled to below 50 ℃, transferring the reaction liquid to 135g of deionized water, and precipitating to separate out a product;
d) Filtering and separating the precipitated product, repeatedly washing and filtering by using heated deionized water at 85 ℃, and finishing washing when the conductivity of the filtrate is detected to be 30 us/cm;
e) And (3) drying the filtered product in a drying oven at the set temperature of 100 ℃ for 12 hours to obtain the aminophenoxy phthalonitrile resin.
And, a method for preparing an aminophenoxy phthalonitrile polymer, comprising the steps of:
a) Coating the amino phenoxy phthalonitrile resin on a quartz glass slide, and placing the quartz glass slide in a drying oven for pretreatment for 10 minutes at 140 ℃;
b) And after the sample is spread on a glass slide, raising the temperature to 200 ℃, and carrying out heat treatment for 1 hour to prepare the aminophenoxy phthalonitrile polymer.
Comparative example 2
A synthetic method of amino phenoxy phthalonitrile resin comprises the following steps:
a) Adding 10.91g of m-aminophenol, 17.3g of 4-nitrophthalonitrile, 13.94g of potassium carbonate and 40g of N, N-dimethylformamide into a three-necked bottle, and stirring and mixing uniformly at room temperature;
b) Slowly heating to the set temperature of 80 ℃, and keeping stirring for continuous reaction for 6 hours;
c) After the reaction system is naturally cooled to below 50 ℃, transferring the reaction liquid to 135g of deionized water, and precipitating to separate out a product;
d) Filtering and separating the precipitated product, repeatedly washing and filtering by using heated deionized water at 85 ℃, and finishing washing when the conductivity of the filtrate is detected to be 30 us/cm;
e) And (3) drying the filtered product in a drying oven at the set temperature of 110 ℃ for 12 hours to obtain the aminophenoxy phthalonitrile resin.
And, a method for preparing an aminophenoxy phthalonitrile polymer, comprising the steps of:
a) Coating the amino phenoxy phthalonitrile resin on a quartz glass slide, and placing the quartz glass slide in a drying oven for pretreatment for 20 minutes at 120 ℃;
b) And after the sample is spread on a glass slide, raising the temperature to 200 ℃, and carrying out heat treatment for 2 hours to prepare the aminophenoxy phthalonitrile polymer.
Comparative example 3
A synthetic method of amino phenoxy phthalonitrile resin comprises the following steps:
a) Adding 10.91g of m-aminophenol, 17.3g of 4-nitrophthalonitrile, 13.94g of potassium carbonate and 40g of N, N-dimethylformamide into a three-necked bottle, and stirring and mixing uniformly at room temperature;
b) Slowly heating to the set temperature of 90 ℃, and keeping stirring for continuous reaction for 5 hours;
c) After the reaction system is naturally cooled to below 50 ℃, transferring the reaction liquid to 135g of deionized water, and precipitating to separate out a product;
d) Filtering and separating the precipitated product, repeatedly washing and filtering by using heated deionized water at 85 ℃, and finishing washing when the conductivity of the filtrate is detected to be 30 us/cm;
e) And (3) drying the filtered product in a drying oven at the set temperature of 100 ℃ for 12 hours to obtain the aminophenoxy phthalonitrile resin.
And, a method for preparing an aminophenoxy phthalonitrile polymer, comprising the steps of:
a) Coating the amino phenoxy phthalonitrile resin on a quartz glass slide, and placing the quartz glass slide in a drying oven for pretreatment for 20 minutes at 130 ℃;
b) And after the sample is spread on a glass slide, raising the temperature to 200 ℃, and carrying out heat treatment for 2 hours to prepare the aminophenoxy phthalonitrile polymer.
The aminophenoxy phthalonitrile resin prepared in the above examples 1 to 5 and comparative example and aminophenoxy phthalonitrile polymer were subjected to the test of yield, potassium ion content and dielectric properties, and the specific test procedures were as follows:
the yield was calculated as: actual product mass/theoretical product mass is calculated by a method of 100%, and the content of potassium ions is detected by adopting a sodium tetraphenylborate gravimetric method by referring to a standard GB/T8574-1988; the dielectric property test is to test the sheet sample by referring to the standard GB 1409-88; thermal float test the heat stress resistance of the sheet samples was tested according to the standard GB/T2423.32-1985.
The color of the resin samples prepared in the above examples 1-5 can reflect the purity of the system to some extent, and the darker the color, the more impurities are present in the system; the yield is used for indicating the yield of the reaction, and the higher the yield is, the more sufficient and thorough the reaction is carried out; the potassium ion content is used for indicating the metal ion content in the resin sample, the metal ion content can directly influence the electrical property of the subsequent polymer, and the lower the content is, the better the purification effect is and the better the electrical property performance is; the moisture content is used to indicate the degree and effect of drying, with lower content indicating more complete drying; the dielectric constant and the dielectric loss of the polymer are used for evaluating the electrical property of the polymer, and the smaller the dielectric constant and the loss are, the more regular the microstructure of the polymer system is, and the larger the application potential in the field of dielectric materials is; the thermal float welding time is used for explaining the thermal stability of the polymer and evaluating the structural stability of the polymer in the processing of the copper-clad plate, and the thermal float welding time is more than 120min, which shows that the thermal performance requirement of the processing of the copper-clad plate on the composite material is completely met.
Specifically, the resin sample prepared in example 1 is yellow powder, the yield is 95.3%, the potassium ion content is less than 500ppm, the moisture content is less than 0.2%, the dielectric constant of the polymer is 3.3 (3 GHz), the dielectric loss is 0.008 (3 GHz), and the hot float welding time is more than 120min, which indicates that the polymer has outstanding thermal stability.
The resin sample prepared in example 2 was a yellow powder with a yield of 95.5%, a potassium ion content of less than 400ppm, a moisture content of less than 0.2%, a polymer dielectric constant of 3.3 (3 GHz), a dielectric loss of 0.008 (3 GHz), and a hot float welding time of more than 120min, indicating that the polymer had outstanding thermal stability.
The resin sample prepared in example 3 was a yellow powder with a yield of 95.2%, a potassium ion content of less than 500ppm, a moisture content of less than 0.2%, a polymer dielectric constant of 3.3 (3 GHz), a dielectric loss of 0.008 (3 GHz), and a hot float welding time of more than 120min, indicating that the polymer had outstanding thermal stability.
The resin sample prepared in example 4 was a yellow powder with a yield of 95.6%, a potassium ion content of less than 300ppm, a moisture content of less than 0.2%, a polymer dielectric constant of 3.3 (3 GHz), a dielectric loss of 0.008 (3 GHz), and a hot float welding time of more than 120min, indicating that the polymer had outstanding thermal stability.
The resin sample prepared in example 5 was a yellow powder with a yield of 95.8%, a potassium ion content of less than 300ppm, a moisture content of less than 0.2%, a polymer dielectric constant of 3.2 (3 GHz), a dielectric loss of 0.007 (3 GHz), and a hot float time of greater than 120min, indicating that the polymer had outstanding thermal stability.
However, the comparative examples respectively carry out comparison experiments in four aspects of raw material proportion, reaction temperature, pretreatment temperature and heat treatment forming time, and the results show that the raw material proportion and the reaction temperature can seriously affect the yield and the product state of the product, the yield is reduced, and whether the direct relation of the pretreatment temperature for darkening the appearance color of the product can prepare the polymer for detection or not; the heat treatment forming time is also directly the cross-linking reaction of the resin system, and influences the thermal stability of the polymer.
Specifically, the resin sample prepared in comparative example 1 is yellow powder, the yield is 92.1%, the potassium ion content is less than 500ppm, the moisture content is less than 0.2%, the dielectric constant of the polymer is 3.4 (3 GHz), the dielectric loss is 0.008 (3 GHz), the thermal float welding time is 70 minutes and is less than 120 minutes, and the thermal stability of the polymer is poor.
The resin sample prepared in comparative example 2 was a yellow powder with a yield of 95.3%, a potassium ion content of less than 500ppm, a moisture content of less than 0.2%, and a poor spreading effect of the pretreatment, and it was not possible to prepare a flat sheet material for testing dielectric characteristics and thermal float welding.
The resin sample prepared in comparative example 3 was a dark yellow powder with a yield of 93.7%, a potassium ion content of less than 500ppm, a moisture content of less than 0.2%, a polymer dielectric constant of 3.5 (3 GHz), a dielectric loss of 0.009 (3 GHz), and a hot float time of greater than 120min, indicating that the polymer had outstanding thermal stability.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. An amino phenoxy phthalonitrile resin is characterized in that the structure of the resin is shown as formula 1:
2. a method for synthesizing an aminophenoxy phthalonitrile resin according to claim 1, comprising the steps of:
1) Adding m-aminophenol, 4-nitrophthalonitrile, potassium carbonate and N, N-dimethylformamide into a three-necked bottle in proportion, and stirring and mixing at room temperature to obtain a mixed solution for later use;
2) Slowly heating the mixed solution to 60-80 ℃, and keeping stirring for continuous reaction for 5-8 hours to obtain a reaction solution;
3) After the reaction system is naturally cooled to below 50 ℃, transferring the reaction liquid into sufficient deionized water, and precipitating to separate out a product;
4) Filtering and separating the precipitated product, then repeatedly washing and filtering by adopting heated deionized water at the temperature of 80-90 ℃, and finishing washing when the conductivity of the filtrate is detected to be lower than 30 us/cm;
5) Drying the product filtered in the step 4), setting the temperature at 90-110 ℃, and drying for 8-12 hours to obtain the amino phenoxy phthalonitrile resin.
3. The method for synthesizing an aminophenoxy phthalonitrile resin according to claim 2, wherein in step 1), the molar ratio of the m-aminophenol, 4-nitrophthalonitrile and potassium carbonate is 1.01: (0.8-1.2).
4. The method for synthesizing aminophenoxy phthalonitrile resin according to claim 2, wherein the slow temperature increase rate in the step 2) is 5 to 10 ℃/min; in the step 3), the weight of the added deionized water is 4-6 times of the weight of the N, N-dimethylformamide.
5. A method for preparing an aminophenoxy phthalonitrile polymer, comprising the steps of:
(A) Coating the aminophenoxy phthalonitrile resin synthesized in claim 2 on a quartz slide glass, and pretreating for 10-20 minutes in a drying oven at 130-150 ℃ for later use;
(B) And after the resin is spread on a glass slide, raising the temperature to 200 ℃, and carrying out heat treatment for 2-4 hours to obtain the aminophenoxy phthalonitrile polymer.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6590118B1 (en) * | 1999-09-29 | 2003-07-08 | Novo Nordisk A/S | Aromatic compounds |
| CN102504252A (en) * | 2011-11-18 | 2012-06-20 | 电子科技大学 | Amino phenoxy phthalonitrile pre-polymer, condensate and preparation method and application thereof |
| CN103193977A (en) * | 2013-04-01 | 2013-07-10 | 河北工业大学 | Method for curing poly benzonitrile resin by amino phenoxy phthalonitrile |
| CN103756312A (en) * | 2013-12-19 | 2014-04-30 | 成都德美精英化工有限公司 | Low-density high temperature resistant cyano resin composite material and preparation method thereof |
| CN109593070A (en) * | 2018-11-14 | 2019-04-09 | 广东汕头超声电子股份有限公司覆铜板厂 | Nitrile-based resin for high-frequency and high-speed copper-clad plate and preparation method thereof |
| CN111875794A (en) * | 2020-07-31 | 2020-11-03 | 成都大学 | Novel preparation method of nitrile resin monomer |
| CN115038747A (en) * | 2020-02-21 | 2022-09-09 | 3M创新有限公司 | Polymerizable compositions, articles, and methods comprising phthalonitrile resins and polyoxometallates |
-
2022
- 2022-09-27 CN CN202211184856.XA patent/CN115650879A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6590118B1 (en) * | 1999-09-29 | 2003-07-08 | Novo Nordisk A/S | Aromatic compounds |
| CN102504252A (en) * | 2011-11-18 | 2012-06-20 | 电子科技大学 | Amino phenoxy phthalonitrile pre-polymer, condensate and preparation method and application thereof |
| CN103193977A (en) * | 2013-04-01 | 2013-07-10 | 河北工业大学 | Method for curing poly benzonitrile resin by amino phenoxy phthalonitrile |
| CN103756312A (en) * | 2013-12-19 | 2014-04-30 | 成都德美精英化工有限公司 | Low-density high temperature resistant cyano resin composite material and preparation method thereof |
| CN109593070A (en) * | 2018-11-14 | 2019-04-09 | 广东汕头超声电子股份有限公司覆铜板厂 | Nitrile-based resin for high-frequency and high-speed copper-clad plate and preparation method thereof |
| CN115038747A (en) * | 2020-02-21 | 2022-09-09 | 3M创新有限公司 | Polymerizable compositions, articles, and methods comprising phthalonitrile resins and polyoxometallates |
| CN111875794A (en) * | 2020-07-31 | 2020-11-03 | 成都大学 | Novel preparation method of nitrile resin monomer |
Non-Patent Citations (2)
| Title |
|---|
| GUO, HENG ETAL: "Self-promoted curing phthalonitrile with high glass transition temperature for advanced composites", 《JOURNAL OF POLYMER RESEARCH》 * |
| ZHOU, HENG ETAL: "Preparation and property comparison of ortho, meta, and para autocatalytic phthalonitrile compounds with amino group", 《 POLYMERS FOR ADVANCED TECHNOLOGIES》 * |
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