1. The phthalonitrile monomer containing the parylene structure is characterized by having the following structural formula:

2. the process for producing a phthalonitrile monomer containing a parylene structure according to claim 1, which comprises the steps of:

(1) uniformly mixing a phenol compound containing a parylene structure, nitrophthalonitrile and a basic catalyst in an organic solvent to obtain a mixed solution for reaction; the molar ratio of the phenol containing a parylene structure, the nitrophthalonitrile and the basic catalyst is 1: 1-2: 1.25-2.5;

(2) under the protection of nitrogen or inert gas, stirring the mixed solution for reaction obtained in the step (1) at the temperature of 60-80 ℃ for reaction for 6-10 hours; then cooling the obtained reaction liquid to room temperature, pouring the reaction liquid into water to separate out a precipitate to obtain a liquid containing the precipitate;

(3) and (3) adjusting the pH value of the liquid containing the precipitate obtained in the step (2) to be neutral, and then carrying out suction filtration, washing and drying to obtain the phthalonitrile monomer containing the parylene structure.

3. The method for preparing a phthalonitrile monomer containing a parylene structure according to claim 2, wherein in the step (1), the structural formula of the phenolic compound containing a parylene structure is as follows:

4. the process for producing a phthalonitrile monomer having a parylene structure according to claim 2 or 3, wherein in the step (1), the nitrophthalonitrile is 4-nitrophthalonitrile or 3-nitrophthalonitrile; the alkaline catalyst is one of anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, sodium hydroxide and potassium hydroxide; the organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone; the organic solvent is metered according to the requirement that 1.9-2.7L of the organic solvent is needed by each mole of the phenol compound containing the parylene structure.

5. The preparation method of the phthalonitrile resin containing the parylene structure is characterized in that the phthalonitrile monomer containing the parylene structure of any one of claims 1 to 4 is melted and foamed, and then is subjected to stepped heating curing reaction at 230-390 ℃ for 12-30 hours to obtain the phthalonitrile resin containing the parylene structure.

6. The method for preparing a phthalonitrile resin containing a parylene structure according to claim 5, wherein the phthalonitrile monomer containing a parylene structure is melted and bubble-removed at 140-200 ℃ under vacuum condition.

7. The preparation method of the phthalonitrile resin containing the parylene structure is characterized in that the phthalonitrile monomer containing the parylene structure prepared by the method of any one of claims 1 to 4 and the traditional phthalonitrile monomer are uniformly mixed, then the obtained mixed material is subjected to melting and bubble removal treatment, and then stepped heating curing reaction is carried out at 230-390 ℃ for 12-30 h, so that the phthalonitrile resin containing the parylene structure is obtained; the phthalonitrile monomer containing the parylene structure accounts for 10-90% of the weight of the traditional phthalonitrile monomer.

8. The method for preparing a phthalonitrile resin containing a parylene structure according to claim 7, wherein the conventional phthalonitrile monomer structure is:wherein the R group is

9. The method for preparing a phthalonitrile resin containing a parylene structure according to claim 7 or 8, wherein a mixed material of a phthalonitrile monomer containing a parylene structure and a conventional phthalonitrile monomer is melted and air bubbles are removed at 140 to 200 ℃ under a vacuum condition.

10. A phthalonitrile resin containing a parylene structure prepared by the process of any one of claims 5 to 9.

Background

Phthalonitrile resin, a high-performance thermosetting resin, was originally developed by the U.S. naval experimental base, and has excellent thermal stability, thermo-mechanical properties, high glass transition temperature, low water absorption and excellent flame retardancy. The properties enable the phthalonitrile resin to have wide application prospects in the fields of composite materials, aerospace, marine ships, electronic packaging and the like.

Researches show that pure phthalonitrile monomer is difficult to crosslink and solidify to form phthalonitrile resin when being processed at high temperature of 280 ℃ for nearly one hundred hours due to factors such as molecular structure rigidity, low reaction activity and the like, so that the processing and application of phthalonitrile resin are greatly limited. Researchers find that active hydrogen compounds such as organic amine, phenol, organic acid, ammonium salt, metal salt and the like can accelerate the curing of the phthalonitrile monomer. However, most of organic amine or phenol curing agents are small molecular compounds, and are easy to volatilize in the curing process, so that defects such as holes and the like are often generated in the material; the metal salt curing agent is difficult to form molecular-level dispersion with phthalonitrile monomer, and metal is easy to oxidize at high temperature, thereby affecting the final performance of the material. Furthermore, pure phthalonitrile monomer tends to show a high melting point, such as 192 ℃ for bisphenol A phthalonitrile monomer and 183 ℃ for m-phenol phthalonitrile monomer, which is not favorable for melt flow and solidification processing of phthalonitrile monomer.

Researchers improve the pure phthalonitrile monomer, namely, special alkyl, hydroxyl or amino groups and other groups are introduced into the phthalonitrile monomer, so that the phthalonitrile monomer has certain autocatalysis characteristic, and the using amount of a curing agent is reduced. However, the melting point of the modified phthalonitrile monomer is still high, for example, the melting point of m-aminophenol type phthalonitrile is 175 ℃, the melting point of bisphenol F type phthalonitrile is 197 ℃, and the processability is still to be improved.

Therefore, the design and synthesis of high-performance phthalonitrile monomers with a novel structure, which have a low melting point, excellent heat resistance and thermal stability, and autocatalytic properties, remain a focus of attention in this field.

In addition, the development of high temperature resistant materials having excellent dielectric properties has been receiving attention as electronic devices are being miniaturized, functionalized and lightened. However, the dielectric properties of the conventional phthalonitrile resin are poor, and the conventional phthalonitrile resin cannot be well applied to the field of functional resin materials.

Disclosure of Invention

The invention aims to provide a self-catalytic phthalonitrile monomer containing a parylene structure and a preparation method thereof, as well as phthalonitrile resin containing the parylene structure and a preparation method thereof, aiming at the technical problems that the traditional phthalonitrile monomer is difficult to cure and the dielectric property of the phthalonitrile resin obtained by curing is not ideal.

The structural formula of the phthalonitrile monomer containing the parylene structure is as follows:

the phthalonitrile monomer containing a parylene structure contains a parylene structure (Wherein various chemical groups can be connected on the benzene ring and the alkyl chain). Parylene (Parylene) is a generic name for Parylene and derivatives thereof, and is a special polymer material with excellent electrical insulation, chemical resistance and uniform coating. The parylene has excellent dielectric property and can be widely applied to the fields of aerospace, military electronics, microelectronics and semiconductors. The traditional processing mode of parylene mainly adopts vacuum vapor deposition, however, vacuum vapor deposition equipment is expensive, processing technology is complex, monomer utilization efficiency is low, the processing method has strict requirements on the cleanliness and surface energy of the surface of a base material, and the product has higher cost. The invention introduces the parylene structure into the phthalonitrile monomer, thereby not only melting the monomerThe point is reduced, the self-catalysis performance and the thermal stability are excellent, the parylene structure unit can also generate ring-opening reaction in the heating and curing process, the formed polymer phthalonitrile resin has excellent dielectric property, and the application field of the polymer phthalonitrile resin is expanded. In addition, the phthalonitrile monomer can also be used as a curing agent, and compared with a common binary aromatic amine or phenol curing agent, the molecular structure of the phthalonitrile monomer has smaller difference with the molecular structure of the traditional phthalonitrile monomer, and can realize better blending effect.

The preparation method of the phthalonitrile monomer containing the parylene structure comprises the following steps:

(1) uniformly mixing a phenol compound containing a parylene structure, nitrophthalonitrile and a basic catalyst in an organic solvent to obtain a mixed solution for reaction; the molar ratio of the parylene-structure-containing phenolic compound to the nitrophthalonitrile to the basic catalyst is 1: 1-2: 1.25-2.5;

(2) under the protection of nitrogen or inert gas, stirring the mixed solution for reaction obtained in the step (1) at 60-80 ℃ for 6-10 hours, then cooling the obtained reaction solution to room temperature, pouring the reaction solution into water, and separating out a precipitate to obtain a precipitate-containing liquid;

(3) and (3) adjusting the pH value of the liquid containing the precipitate obtained in the step (2) to be neutral, and then carrying out suction filtration, washing and drying to obtain the phthalonitrile monomer containing the parylene structure.

In the step (1), the structural formula of the parylene-structured phenolic compound is as follows:

in the step (1), the nitrophthalonitrile is 4-nitrophthalonitrile or 3-nitrophthalonitrile.

In the step (1), the basic catalyst is one of anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium bicarbonate, sodium hydroxide, potassium hydroxide and the like.

In the step (1), the organic solvent is one of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP). The organic solvent is metered according to the requirement that 1.9-2.7L of the organic solvent is needed by each mole of the parylene structure phenolic compound.

In the step (2), the inert gas is helium, neon, argon or xenon.

In the step (2), the water used for precipitating the reaction solution obtained by the reaction is not strictly required, and may be tap water, deionized water or distilled water, preferably deionized water at room temperature, and is measured by using deionized water with a volume of about 8-12 times per 100 ml of the reaction solution.

The preparation method of the phthalonitrile resin containing the parylene structure of the present invention includes the following two methods, which belong to a general inventive concept.

1. Phthalonitrile resin prepared by using phthalonitrile monomer containing parylene structure as raw material

The method comprises the steps of melting a phthalonitrile monomer containing a parylene structure, removing bubbles, and carrying out stepped heating curing reaction at 230-390 ℃ for 12-30 h to obtain phthalonitrile resin containing the parylene structure.

In the method, the phthalonitrile monomer containing the parylene structure is melted at 140-200 ℃ under the vacuum condition and bubbles are removed; generally, no bubbles are discharged, and the time is about 15-25 min.

In the method, the step heating curing procedure comprises the following steps:

keeping the temperature for 2-5 h at the temperature T of more than or equal to 230 ℃ and less than or equal to 240 ℃;

keeping the temperature for 2-5 h at the temperature T of more than or equal to 260 ℃ and less than or equal to 270 ℃;

keeping the temperature for 2-5 h at T of more than 290 ℃ and less than or equal to 300 ℃;

keeping the temperature for 2-5 h at the temperature T of more than or equal to 320 ℃ and less than or equal to 330 ℃;

keeping the temperature for 2-5 h at the temperature T of more than or equal to 340 ℃ and less than or equal to 360 ℃;

keeping the temperature for 2-5 h at the temperature T of more than or equal to 370 ℃ and less than or equal to 390 ℃.

2. Phthalonitrile resin prepared by using phthalonitrile monomer containing parylene structure and traditional phthalonitrile monomer as raw materials

Uniformly mixing a phthalonitrile monomer containing a parylene structure with a traditional phthalonitrile monomer, melting the obtained mixed material, removing bubbles, and carrying out stepped heating curing reaction at 230-390 ℃ for 12-30 h to obtain phthalonitrile resin containing the parylene structure; the phthalonitrile monomer containing the parylene structure accounts for 10-90% of the weight of the traditional phthalonitrile monomer.

In the above method, the structure of the conventional phthalonitrile monomer is:wherein the R group is

In the method, a mixed material containing a phthalonitrile monomer with a parylene structure and a traditional phthalonitrile monomer is melted at 140-200 ℃ under a vacuum condition and bubbles are removed; generally, no bubbles are discharged, and the time is about 15-25 min.

In the method, the step heating curing procedure comprises the following steps:

keeping the temperature for 2-5 h at the temperature T of more than or equal to 230 ℃ and less than or equal to 240 ℃;

keeping the temperature for 2-5 h at the temperature T of more than or equal to 260 ℃ and less than or equal to 270 ℃;

keeping the temperature for 2-5 h at T of more than 290 ℃ and less than or equal to 300 ℃;

keeping the temperature for 2-5 h at the temperature T of more than or equal to 320 ℃ and less than or equal to 330 ℃;

keeping the temperature for 2-5 h at the temperature T of more than or equal to 340 ℃ and less than or equal to 360 ℃;

keeping the temperature for 2-5 h at the temperature T of more than or equal to 370 ℃ and less than or equal to 390 ℃.

The phthalonitrile resin containing the parylene structure is prepared by the two methods.

The phthalonitrile monomer containing the parylene structure, the phthalonitrile resin and the preparation method thereof have the following beneficial effects:

(1) according to the invention, a phenol compound containing a parylene structure and nitrophthalonitrile are used as raw materials, and react under the action of an alkaline catalyst to obtain a phthalonitrile monomer containing the parylene structure, the parylene structure is introduced into the phthalonitrile structure for the first time, and the prepared phthalonitrile monomer containing the parylene structure has an autocatalysis effect and can be effectively cured and formed in a heating and curing process, so that the resin defect caused by volatilization of a small molecular curing agent is avoided.

(2) According to the phthalonitrile monomer containing the parylene structure, the benzene ring and the aliphatic chain structure in the introduced parylene structure can be connected with various chemical groups through chemical reaction, and the derived parylene structure is diversified, so that the designability of the phthalonitrile monomer structure is enhanced.

(3) The phthalonitrile monomer containing the parylene structure can be used as a curing agent of the traditional phthalonitrile monomer, and can realize better blending effect due to smaller molecular structure difference with the traditional phthalonitrile monomer.

(4) The phthalonitrile resin containing the parylene structure has higher thermal decomposition temperature (T) in a nitrogen atmosphere_5％) And a higher char yield, and thus it exhibits excellent thermal properties.

(5) The phthalonitrile resin containing the parylene structure provided by the invention has excellent dielectric property due to the parylene structure, and can expand the application of the phthalonitrile resin in the fields of aerospace, military electronics, microelectronics, semiconductors and the like.

(6) The phthalonitrile monomer containing the parylene structure is also a derivative monomer of the parylene structure, and the melting point of the phthalonitrile monomer is only about 130 ℃, so that the phthalonitrile monomer can be formed by hot processing, and compared with expensive vacuum vapor deposition equipment and strict and harsh processing conditions required by a traditional vacuum vapor deposition processing method of the parylene structure, the derivative monomer is simpler and more convenient to process and has lower cost.

(7) The preparation method of the phthalonitrile monomer and phthalonitrile resin containing the parylene structure provided by the invention has the advantages of simple process, easily obtained raw materials and contribution to industrial production.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of the phthalonitrile monomer containing a parylene structure prepared in example 1.

FIG. 2 is a DSC chart of the phthalonitrile monomer containing the parylene structure prepared in example 1.

FIG. 3 is a TGA profile of the nitrogen atmosphere of the phthalonitrile monomer containing a parylene structure prepared in example 1.

FIG. 4 is a TGA profile of a nitrogen atmosphere of the phthalonitrile resin containing a parylene structure prepared in example 1.

FIG. 5 is a graph showing the dielectric constant and dielectric loss of the parylene structure-containing phthalonitrile resin prepared in example 1.

Detailed Description

The technical solution of the present invention is further described below by way of examples with reference to the accompanying drawings.

Example 1

1. Preparation of phthalonitrile monomer containing parylene structure

In the present embodiment, a parylene structure-containing phenolic compound 1 (compound 1 for short: its synthetic process reference: Photochromym of novel chromenes constrained to part of [2.2] paracyclophane: remarkable's ' of ' plants on the colorodid o-quinoid intermediates (DOI:10.1039/c2nj40 40575j)) and 4-nitrophthalonitrile are used as raw materials, and anhydrous potassium phosphate is used as a catalyst to prepare a phthalonitrile monomer containing a parylene structure, wherein the synthetic route is as follows:

the preparation steps are as follows:

(1) adding 10g (44.58mmol) of compound 1, 7.72g (44.58mmol) of 4-nitrophthalonitrile and 7.70g (55.73mmol) of anhydrous potassium carbonate into a reactor, adding 84ml of DMSO, and uniformly mixing to obtain a mixed solution for reaction;

(2) under the protection of nitrogen, heating the mixed solution for reaction to 80 ℃, and reacting for 6 hours under the condition of magnetic stirring; then cooling the obtained reaction liquid to room temperature, and pouring the reaction liquid into 1L of room-temperature deionized water to separate out a precipitate to obtain a liquid containing the precipitate;

(3) and (2) adjusting the pH value of the liquid containing the precipitate to 7 by using dilute hydrochloric acid with the concentration of 1mol/L, then carrying out vacuum filtration to obtain the precipitate, cleaning the precipitate by using deionized water until the filtrate is clear and transparent, and finally carrying out vacuum drying on the cleaned precipitate at 80 ℃ for 24h to obtain the phthalonitrile monomer containing the parylene structure, wherein the yield is 75%.

2. Preparation of phthalonitrile resin containing parylene structure

And (2) placing phthalonitrile monomer powder containing the parylene structure prepared by the method in an aluminum foil mold, heating the powder to 140 ℃ for melting in a vacuum oven, removing bubbles in vacuum at the temperature for 20min, transferring the powder to a muffle furnace, and completing solidification according to a step heating program of heat preservation at 230 ℃ for 5h, heat preservation at 270 ℃ for 5h, heat preservation at 300 ℃ for 3h, heat preservation at 325 ℃ for 3h, heat preservation at 350 ℃ for 3h and heat preservation at 375 ℃ for 5h, and finally cooling the powder to room temperature along with the furnace to obtain the phthalonitrile curing resin containing the parylene structure.

The pyroxylonitrile monomer containing the parylene structure prepared in example 1 was subjected to nuclear magnetic hydrogen spectroscopy, and the analysis results are shown in fig. 1, and δ ═ 8.03(d, J ═ 8.8Hz,1H),7.77(d, J ═ 2.6Hz,1H),7.29(dd, J ═ 8.8,2.6Hz,1H),7.06(dd, J ═ 7.8,1.9Hz,1H),6.66-6.52(m,3H),6.47(ddd, J ═ 13.2,7.8,1.9Hz,2H),6.05(d, J ═ 1.7Hz,1H),3.07-2.90(m,6H),2.90-2.79(m,1H),2.71-2.59(m,1H), and the synthesis of the monomer was successful.

The phthalonitrile monomer containing the parylene structure prepared in example 1 was analyzed by DSC (Differential Scanning calorimetry) and the results are shown in FIG. 2. As can be seen from FIG. 2, the phthalonitrile monomer containing the parylene structure has a melting point of 133 deg.C and a distinct exothermic curing peak at 309 deg.C. The monomer structure can be effectively cured and molded in the heating curing process.

Thermogravimetric analysis (TGA) was performed on the phthalonitrile monomer containing a parylene structure prepared in example 1 under a nitrogen atmosphere, and the analysis results are shown in fig. 3. As can be seen from the TGA curve in FIG. 3, the char yield of the phthalonitrile monomer containing a parylene structure at 800 ℃ under a nitrogen atmosphere is 67.9%, which also indicates that the monomer structure undergoes a rapid curing reaction during the temperature rise process, resulting in a higher char yield.

Thermogravimetric analysis (TGA) was performed on the phthalonitrile resin containing a parylene structure prepared in example 1 under a nitrogen atmosphere, and the analysis results are shown in fig. 4. As can be seen from the TGA curve in FIG. 4, the temperature T corresponding to 5% weight loss of the resin under nitrogen atmosphere after curing_5％The temperature is 489 ℃, and the carbon residue rate at 800 ℃ is 70%. The phthalonitrile resin containing the parylene structure has excellent heat resistance, and can be used as a high-temperature resistant material, a composite material matrix, an adhesive and the like in the fields of microelectronics, aerospace, machinery and the like.

The dielectric property test of the phthalonitrile resin containing the parylene structure prepared in example 1 shows that the dielectric constant at 1kHz is 5.8 and the dielectric loss is 0.0034, as shown in FIG. 5, which shows that the phthalonitrile resin containing the parylene structure prepared in example has good dielectric property.

Example 2

1. Preparation of phthalonitrile monomer containing parylene structure

In the embodiment, a phthalonitrile monomer containing a parylene structure is prepared by taking a phenolic compound 2 containing the parylene structure (compound 2 for short: its synthetic process reference: electro-phenolic customization of 1,1,2,2,9,9,10,10-Octafluoro [2.2] paracyclophane (DOI:10.1021/jo9910536)) and 4-nitrophthalonitrile as raw materials and taking anhydrous sodium phosphate as a catalyst, and the synthetic route is as follows:

the preparation steps are as follows:

(1) adding 16.41g (44.58mmol) of compound 2, 7.72g (44.58mmol) of 4-nitrophthalonitrile and 5.91g (55.73mmol) of anhydrous sodium carbonate into a reactor, adding 84ml of TMAC, and uniformly mixing to obtain a mixed solution for reaction;

(2) under the protection of nitrogen, heating the mixed solution for reaction to 80 ℃, and reacting for 6 hours under the condition of magnetic stirring; then cooling the obtained reaction liquid to room temperature, and pouring the reaction liquid into 1L of room-temperature deionized water to separate out a precipitate to obtain a liquid containing the precipitate;

(3) and (2) adjusting the pH value of the liquid containing the precipitate to 6 by using dilute hydrochloric acid with the concentration of 1mol/L, then carrying out vacuum filtration to obtain the precipitate, cleaning the precipitate by using deionized water until the filtrate is clear and transparent, and finally carrying out vacuum drying on the cleaned precipitate at 80 ℃ for 24h to obtain the phthalonitrile monomer containing the parylene structure, wherein the yield is 80%.

2. Preparation of phthalonitrile resin containing parylene structure

And (2) placing phthalonitrile monomer powder containing the parylene structure prepared by the method in an aluminum foil mold, heating the powder to 180 ℃ in a vacuum oven for melting, removing bubbles in vacuum for 15min at the temperature, transferring the powder to a muffle furnace, and completing solidification according to a step heating program of heat preservation at 230 ℃ for 2h, heat preservation at 260 ℃ for 2h, heat preservation at 290 ℃ for 5h, heat preservation at 320 ℃ for 5h, heat preservation at 350 ℃ for 5h and heat preservation at 380 ℃ for 2h, and finally cooling the powder to room temperature along with the furnace to obtain the phthalonitrile curing resin containing the parylene structure.

The thermal properties of the phthalonitrile resin containing a parylene structure obtained after curing are close to those of example 1.

Example 3

1. Preparation of phthalonitrile monomer containing parylene structure

In the embodiment, a phthalonitrile monomer containing a parylene structure is prepared by taking a phenolic compound 3 containing a parylene structure (compound 3 for short, the synthetic process reference is 3Reactions of nucleotides with Perfluoro [2.2] paracyclophane (DOI:10.1021/jo9014535)) and 4-nitrophthalonitrile as raw materials and taking anhydrous sodium phosphate as a catalyst, and the synthetic route is as follows:

the preparation steps are as follows:

(1) 22.02g (44.58mmol) of compound 3, 7.72g (44.58mmol) of 4-nitrophthalonitrile and 5.91g (55.73mmol) of anhydrous sodium carbonate are added into a reactor, and then 84ml of TMAC is added and mixed uniformly to obtain a mixed solution for reaction;

(2) under the protection of nitrogen, heating the mixed solution for reaction to 80 ℃, and reacting for 6 hours under the condition of magnetic stirring; then cooling the obtained reaction liquid to room temperature, and pouring the reaction liquid into 670 ml of room-temperature deionized water to separate out a precipitate to obtain a liquid containing the precipitate;

(3) and (2) adjusting the pH value of the liquid containing the precipitate to 8 by using dilute hydrochloric acid with the concentration of 1mol/L, then carrying out vacuum filtration to obtain the precipitate, cleaning the precipitate by using deionized water until the filtrate is clear and transparent, and finally carrying out vacuum drying on the cleaned precipitate at 80 ℃ for 24h to obtain the phthalonitrile monomer containing the parylene structure, wherein the yield is 75%.

2. Preparation of phthalonitrile resin containing parylene structure

And (2) placing phthalonitrile monomer powder containing the parylene structure prepared by the method in an aluminum foil mold, heating the phthalonitrile monomer powder to 180 ℃ for melting in a vacuum oven, removing bubbles in vacuum at the temperature for 20min, transferring the phthalonitrile monomer powder to a muffle furnace, and completing solidification according to a step heating program of heat preservation at 230 ℃ for 2h, heat preservation at 260 ℃ for 2h, heat preservation at 290 ℃ for 2h, heat preservation at 320 ℃ for 2h, heat preservation at 350 ℃ for 2h and heat preservation at 380 ℃ for 2h, and finally cooling the phthalonitrile monomer powder to room temperature along with the furnace to obtain the phthalonitrile curing resin containing the parylene structure.

The thermal properties of the phthalonitrile resin containing a parylene structure obtained after curing are close to those of example 1.

Example 4

1. Preparation of phthalonitrile monomer containing parylene structure

In the present embodiment, a parylene structure-containing phenolic compound 1 (compound 1 for short: its synthetic process reference: Photochromym of novel chromenes constrained to part of [2.2] paracyclophane: remarkable's ' of ' medicines on the colored o-quinoid intermediates (DOI:10.1039/c2nj40 40575j)) and 3-nitrophthalonitrile are used as raw materials, and anhydrous potassium phosphate is used as a catalyst to prepare a phthalonitrile monomer containing a parylene structure, and the synthetic route is as follows:

the preparation steps are as follows:

(1) adding 10g (44.58mmol) of compound 1, 7.72g (44.58mmol) of 3-nitrophthalonitrile and 7.70g (55.73mmol) of anhydrous potassium carbonate into a reactor, adding 84ml of DMSO, and uniformly mixing to obtain a mixed solution for reaction;

(2) under the protection of nitrogen, heating the mixed solution for reaction to 80 ℃, and reacting for 6 hours under the condition of magnetic stirring; then cooling the obtained reaction liquid to room temperature, and pouring the reaction liquid into 850 ml of room-temperature deionized water to separate out a precipitate to obtain a liquid containing the precipitate;

(3) and (2) adjusting the pH value of the liquid containing the precipitate to 7 by using dilute hydrochloric acid with the concentration of 1mol/L, then carrying out vacuum filtration to obtain the precipitate, cleaning the precipitate by using deionized water until the filtrate is clear and transparent, and finally carrying out vacuum drying on the cleaned precipitate at 80 ℃ for 24h to obtain the phthalonitrile monomer containing the parylene structure, wherein the yield is 80%.

2. Preparation of phthalonitrile resin containing parylene structure

And (2) placing phthalonitrile monomer powder containing the parylene structure prepared by the method in an aluminum foil mold, heating the powder to 150 ℃ in a vacuum oven for melting, removing bubbles in vacuum for 25min at the temperature, transferring the powder to a muffle furnace, and completing solidification according to a step heating program of heat preservation at 230 ℃ for 3h, heat preservation at 260 ℃ for 3h, heat preservation at 290 ℃ for 3h, heat preservation at 320 ℃ for 3h, heat preservation at 350 ℃ for 3h and heat preservation at 380 ℃ for 3h, and finally cooling the powder to room temperature along with the furnace to obtain the phthalonitrile curing resin containing the parylene structure.

The thermal properties of the phthalonitrile resin containing a parylene structure obtained after curing are close to those of example 1.

Example 5

1. Preparation of phthalonitrile monomer containing parylene structure

In the present example, a parylene structure-containing phenolic compound 4 (compound 4: its synthetic process reference: Photochromym of novel chromenes constrained to part of [2.2] paracyclophane: remarkable's' medicines on the colored o-quinoid intermediates (DOI:10.1039/c2nj40 40575j)) and 4-nitrophthalonitrile are used as raw materials, and anhydrous potassium phosphate is used as a catalyst to prepare a phthalonitrile monomer containing a parylene structure, the synthetic route is as follows:

the preparation steps are as follows:

(1) adding 10.71g (44.58mmol) of compound 4, 15.44g (89.16mmol) of 4-nitrophthalonitrile and 15.40g (111.42mmol) of anhydrous potassium carbonate into a reactor, adding 120ml of DMSO, and uniformly mixing to obtain a mixed solution for reaction;

(2) under the protection of nitrogen, heating the mixed solution for reaction to 60 ℃, and reacting for 10 hours under the condition of magnetic stirring; then cooling the obtained reaction liquid to room temperature, and pouring the reaction liquid into 1L of room-temperature deionized water to separate out a precipitate to obtain a liquid containing the precipitate;

(3) and (2) adjusting the pH value of the liquid containing the precipitate to 7 by using dilute hydrochloric acid with the concentration of 1mol/L, then carrying out vacuum filtration to obtain the precipitate, cleaning the precipitate by using deionized water until the filtrate is clear and transparent, and finally carrying out vacuum drying on the cleaned precipitate at 80 ℃ for 24h to obtain the phthalonitrile monomer containing the parylene structure, wherein the yield is 83%.

2. Preparation of phthalonitrile resin containing parylene structure

And (2) placing phthalonitrile monomer powder containing the parylene structure prepared by the method in an aluminum foil mold, heating the powder to 200 ℃ in a vacuum oven for melting, removing bubbles in vacuum at the temperature for 20min, then transferring the powder to a muffle furnace to finish curing according to a step heating program of preserving heat at 240 ℃ for 5h, preserving heat at 270 ℃ for 5h, preserving heat at 300 ℃ for 5h, preserving heat at 330 ℃ for 5h, preserving heat at 360 ℃ for 5h and preserving heat at 390 ℃ for 5h, and finally cooling the powder to room temperature along with the furnace to obtain the phthalonitrile curing resin containing the parylene structure.

Performing thermogravimetric analysis on the cured phthalonitrile resin containing the parylene structure in a nitrogen atmosphere to obtain T_5％The carbon residue rate was 73% at 498 ℃ and 800 ℃.

Example 6

1. Preparation of phthalonitrile monomer containing parylene structure

In the embodiment, a phthalonitrile monomer containing a parylene structure is prepared by taking phenolic compound 5 containing a parylene structure (compound 5 for short: the synthetic process reference of the compound 5: Octafluoro [2.2] paracyclophane (AF4) quinone (DOI:10.1135/cccc20081764)) and 4-nitrophthalonitrile as raw materials and taking anhydrous sodium bicarbonate as a catalyst, and the synthetic route is as follows:

the preparation steps are as follows:

(1) adding 17.16g (44.58mmol) of compound 5, 15.44g (89.16mmol) of 4-nitrophthalonitrile and 9.36g (111.42mmol) of anhydrous sodium bicarbonate into a reactor, adding 120ml of DMF, and uniformly mixing to obtain a mixed solution for reaction;

(2) under the protection of nitrogen, heating the mixed solution for reaction to 60 ℃, and reacting for 10 hours under the condition of magnetic stirring; then cooling the obtained reaction liquid to room temperature, and pouring the reaction liquid into 1L of room-temperature deionized water to separate out a precipitate to obtain a liquid containing the precipitate;

(3) and (2) adjusting the pH value of the liquid containing the precipitate to 6 by using dilute hydrochloric acid with the concentration of 1mol/L, then carrying out vacuum filtration to obtain the precipitate, cleaning the precipitate by using deionized water until the filtrate is clear and transparent, and finally carrying out vacuum drying on the cleaned precipitate at 80 ℃ for 24 hours to obtain the phthalonitrile monomer containing the parylene structure, wherein the yield is 83%.

2. Preparation of phthalonitrile resin containing parylene structure

And (2) placing phthalonitrile monomer powder containing the parylene structure prepared by the method in an aluminum foil mold, heating the powder to 180 ℃ in a vacuum oven for melting, removing bubbles in vacuum at the temperature for 25min, transferring the powder to a muffle furnace, and completing solidification according to a step heating program of preserving heat at 235 ℃ for 5h, preserving heat at 265 ℃ for 5h, preserving heat at 295 ℃ for 5h, preserving heat at 325 ℃ for 5h, preserving heat at 340 ℃ for 5h and preserving heat at 370 ℃ for 5h, and finally cooling the powder to room temperature along with the furnace to obtain the phthalonitrile curing resin containing the parylene structure.

The thermal properties of the phthalonitrile resin containing a parylene structure obtained after curing are close to those of example 5.

Example 7

Grinding and blending 1g of resorcinol-based phthalonitrile monomer and 0.1g of phthalonitrile monomer containing a parylene structure prepared in example 1 uniformly, then loading the mixture into a mold, then placing the mold into a vacuum oven to be heated to 180 ℃ for melting, removing bubbles in vacuum for 20min at the temperature, transferring the mixture into a muffle furnace after bubbles are removed completely, and finishing curing according to a step heating procedure of heat preservation at 230 ℃ for 2h, heat preservation at 260 ℃ for 2h, heat preservation at 290 ℃ for 2h, heat preservation at 320 ℃ for 2h, heat preservation at 350 ℃ for 2h and heat preservation at 380 ℃ for 2h, and then cooling the mixture to room temperature along with the furnace to obtain phthalonitrile resin containing the parylene structure.

Carrying out thermogravimetric analysis on the obtained phthalonitrile resin in nitrogen atmosphere to obtain T_5％The carbon residue rate at 800 ℃ is 71 percent and is 495 ℃.

Example 8

Grinding and blending 1g of p-phenylene diphenol phthalonitrile monomer and 0.9g of phthalonitrile monomer containing the parylene structure prepared in the embodiment 5 uniformly, then putting the mixture into a mold, then putting the mold into a vacuum oven to be heated to 180 ℃ for melting, removing bubbles in vacuum for 20min at the temperature, after the bubbles are removed completely, transferring the mixture into a muffle furnace to finish solidification according to a step heating program of preserving heat at 235 ℃ for 5h, preserving heat at 265 ℃ for 5h, preserving heat at 295 ℃ for 5h, preserving heat at 325 ℃ for 5h, preserving heat at 355 ℃ for 5h and preserving heat at 385 ℃ for 5h, and then cooling the mixture to room temperature along with the furnace to obtain the phthalonitrile resin containing the parylene structure.

Carrying out thermogravimetric analysis on the obtained phthalonitrile resin in nitrogen atmosphere to obtain T_5％The carbon residue rate at 800 ℃ is 75 percent at 501 ℃.

Example 9

Grinding and blending 1g of bisphenol A-based phthalonitrile monomer and 0.5g of the phthalonitrile monomer containing the parylene structure prepared in the embodiment 4 uniformly, then putting the mixture into a mold, then putting the mold into a vacuum oven to be heated to 180 ℃ for melting, removing bubbles in vacuum for 15min at the temperature, after the bubbles are removed completely, transferring the mixture into a muffle furnace to finish solidification according to a step heating procedure of heat preservation at 230 ℃ for 2h, heat preservation at 260 ℃ for 2h, heat preservation at 290 ℃ for 2h, heat preservation at 320 ℃ for 2h, heat preservation at 350 ℃ for 2h and heat preservation at 380 ℃ for 2h, and then cooling the mixture to room temperature along with the furnace to obtain the phthalonitrile resin containing the parylene structure.

Thermogravimetric analysis is carried out on the obtained phthalonitrile resin in nitrogen atmosphere, T_5％The carbon residue rate at 800 ℃ is 69 percent at 490 ℃.

It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.