CN113307967A - Polyaramide material containing adamantyl groups, and preparation method and application thereof - Google Patents
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- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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Abstract
The invention discloses a polyaramide material containing adamantyl groups, and a preparation method and application thereof. On the basis of excellent mechanical property, solvent resistance, flame retardance and heat resistance of the traditional polyaramide, the invention introduces a bulky aliphatic cage group of adamantane on a main chain aromatic ring, reduces intermolecular force, increases intermolecular distance and reduces crystallization property, thereby increasing the free volume of a polymer chain, improving the solubility of the polyaramide, leading the polyaramide to be easier to process and form and simultaneously reducing the dielectric constant of the polyaramide material. The method for preparing the polyaramide material by low-temperature prepolymerization has the advantages of simple operation, mild conditions, simple and convenient monomer synthesis, easy large-scale production and wide application prospect in the aspects of low dielectric materials such as dielectric insulating layer materials, communication antenna coating materials, 5G base station coating and protective materials and the like.
Description
Technical Field
The invention relates to a polyaramide material, in particular to a polyaramide material containing adamantyl groups, which is mainly applied to the aspects of dielectric insulating layer materials, communication antenna coating materials, high-performance fibers and the like, and belongs to the field of material chemistry.
Background
With the rapid development of the communication industry, the 5G era has come. The millimeter wave band is adopted in 5G communication, and as the wavelength of electromagnetic waves is shorter, the diffraction capability is poorer, and the attenuation in the propagation process is gradually increased. From maxwell's equations and their derivation, it can be known that the higher the dielectric constant value of the material, the smaller the transmission speed of the electromagnetic signal, the more significant the delay, and the higher the loss. In order to improve the signal transmission speed, signal delay, signal loss, etc. of 5G communication, it is necessary to develop a novel material having a low dielectric constant.
Polyaramid is a high-performance polymer formed by the reaction and polycondensation of aromatic diamine and diacid, has excellent mechanical properties, solvent resistance, flame retardance and heat resistance due to intermolecular hydrogen bonds and a rigid structure of main chain aromatic, and is widely applied to the fields of high-performance fibers, dielectric insulating layers in large-scale integrated circuits and the like. However, the dielectric constant of the polyaramid material used conventionally is usually more than 3, which has strong signal-blocking ability and has a great influence when applied to communication and integrated circuits. Therefore, the dielectric constant of the material needs to be further reduced on the basis of ensuring the performance of the material, so that the material can be better applied to insulating materials.
The dielectric constant of the polymer can be reduced by regulating the structure of the polymer. The dielectric constant is related to the polarity of the polymer molecules, and simply speaking, the introduction of the low-polarizability and large-volume aliphatic structural unit into the structure of the polyaramid material can effectively reduce the dielectric constant. Adamantane is a class of aliphatic cage-like molecules with a large volume, which have a low polarizability and are themselves low dielectric constant materials. The free volume of the polymer chain can be increased by reducing intermolecular force, increasing intermolecular distance and reducing crystallization performance so as to realize reduction of dielectric constant.
Disclosure of Invention
The invention aims to develop a novel polyaramide material, which is mainly realized by modifying the chemical structure of polyaramide and introducing an adamantane derivative to the main chain of the polyaramide. The introduction of bulky aliphatic cage-like molecular adamantane can reduce the acting force between polymer chains, increase the distance between molecules, increase the free volume of the polymer chains and further reduce the dielectric constant of the polymer chains. Meanwhile, due to the introduction of bulky side groups, the solubility of the polyaramid can be increased, and the processability of the polyaramid is improved. The novel polyaramide material has wide application prospect in the aspects of dielectric insulating layer materials, communication antenna coating materials, 5G base station coating and protective materials and the like.
Specifically, the invention adopts a new method for regulating and modifying the chemical structure of the polymer, and improves the chemical composition of the polymer. The polyaramid is formed by the reaction and polymerization of aromatic diacid containing required structural units and aromatic diamine, and the properties of the finally polymerized material can be controlled by modifying the structures of the diamine and the diacid, so that specific functions are met. The introduction of low polarizability groups or bulky aliphatic groups into their molecular structure is of major concern. The introduction of the groups can reduce the polarity of molecules, increase the free volume of molecular chains and reduce the molecular chain stacking capacity, so that the polyaramide with lower dielectric constant is expected to be obtained. More importantly, the conventional polyaramid has strong intermolecular interaction and high molecular chain rigidity, and although the acting force endows the polyaramid with excellent comprehensive performance, the polyaramid also has the problems of poor solubility, high glass transition temperature and the like, and brings difficulty to molding processing. The dense packing structure of a molecular chain can be destroyed by introducing bulky substituent groups into the side groups of the benzene ring, and the solubility and the processability are improved. Therefore, the polyaramid containing the adamantyl group has larger improvement and improvement on the polymer processing performance.
The purpose of the invention is realized by the following technical scheme:
a polyaramid material containing adamantyl groups, consisting of comonomer units of formula I:
in the formula I, Ar1Is selected from
One or more of; ar (Ar)2Is selected from
One or more of; n is an integer between 50 and 1000.
According to the invention, the polyaramid material containing adamantyl groups can be a homopolymer or Ar1And Ar2Among them, a copolymer obtained by mixing and selectively copolymerizing a plurality of aromatic rings.
The invention also provides a preparation method of the polyaramide material containing adamantyl groups, and the polyaramide material can be prepared by a low-temperature prepolymerization method:
preferably, the ClOC-Ar is mixed under ice-bath conditions1-COCl and H2N-Ar2-NH2Dissolving in polar organic solvent such as N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), Dimethylformamide (DMF), dimethylacetamide (DMAc), NMP-LiCl or DMF-LiCl salt solution, performing solution polycondensation, and performing prepolymerization for 30-60 min; removing the ice bath and reacting at 20-60 deg.C for a period of time, such as 0.5-48 hours (preferably 1-24 hours); and dripping the reaction solution into water at the temperature of 90-100 ℃ for precipitation, removing the salt, dissolving the solution with a good solvent, dripping the solution into methanol or ethanol for precipitation, filtering and drying to obtain the polyaramide material. Wherein Ar is1And Ar2Is as defined above.
According to the invention, in the low-temperature prepolymerization preparation method, the polymerization reaction temperature after removing the ice bath can be 25 ℃, 40 ℃, 50 ℃ or 60 ℃ and the like, and the reaction time can be 0.5 hour, 1 hour, 2 hours and the like till 48 hours. In the polar solvent-LiCl solution, the mass percent concentration of LiCl is between 1 and 8 percent.
The invention also provides the application of the polyaramide material, which can be used for spinning and film forming, can also be used for preparing strips, hollow tubes and the like, and has wide application prospect in the aspects of preparing dielectric insulating layer materials, communication antenna coating materials, 5G base station coating and protective materials and the like as low dielectric materials.
Compared with the existing material, the polyaramide material containing the adamantyl groups provided by the invention has excellent performance, and the advantages are specifically represented as follows:
1) the polyaramid material greatly improves the solubility of the polymer due to the reduction of molecular chain regularity, can be dissolved in organic solvents such as NMP, DMSO, DMAc, NMP-LiCl or DMF-LiCl and the like, and improves the processability of the polymer;
2) the preparation method of the polyaramide provided by the invention is simple, mild in condition, simple and convenient in monomer synthesis, low in price and easy for industrial large-scale production;
3) the polyaramide material has low dielectric constant, and can be widely applied to the preparation of dielectric insulating layer materials, communication antenna coating materials, 5G base station coating and protective materials.
Drawings
FIG. 1 is a schematic view of the structural formula of the polyaramid material of the present invention.
FIG. 2 shows the results of Gel Permeation Chromatography (GPC) of the polymer of formula II synthesized in the examples of the present invention.
FIG. 3 is a graph of the thermogravimetric plot of the polymer of formula II synthesized in the example of the present invention.
FIG. 4 shows the dielectric constant (a) and dielectric loss values (b) at different frequencies for the polymer of formula II synthesized by the example of the present invention.
FIG. 5 is a tensile stress-strain curve of a sample of polymer film of formula II synthesized in accordance with an embodiment of the present invention.
Detailed Description
The invention is further described below by means of specific examples, without restricting the scope of the invention in any way.
Example 1 Synthesis of the polyaramid represented by the formula II
Step 1: synthesis of 5- (1-adamantyl) -1, 3-xylene
A500 mL dry flask was charged with 10.6g of m-xylene, 15.2g of 1-adamantanol, and 200mL of trifluoroacetic acid. Then, the mixture was stirred at room temperature for 24min, and a white solid was precipitated. After the reaction was completed, the solid product was collected by filtration and washed three times with deionized water. Yield 20.2g, 78.3%.1H NMR:1.80(m,6H)；1.92(m,6H)；2.12(m,3H)；2.35(s,6H)；6.86(s,1H)；7.02(s,2H)。
Step 2: synthesis of 5- (1-adamantyl) -isophthalic acid
In a 500mL dry flask were added 4.8g of 5- (1-adamantyl) -1, 3-xylene, 16g of potassium permanganate, 200mL of pyridine, and 35mL of water. Heating to reflux reaction until the purple potassium permanganate is removed, adding 8g of potassium permanganate and 20mL of water in two batches, and continuing to react for 24 hours after the potassium permanganate is added. After the reaction is finished, insoluble solids are removed by filtration, and if the filtrate is mauve, sodium bisulfite is added to reduce the residual potassium permanganate. And dropwise adding hydrochloric acid into the filtrate under stirring until the filtrate is acidic, and filtering to collect a solid product. The solid product obtained is dissolved again by NaOH aqueous solution, and the solution is alkaline. Insoluble impurities were removed by filtration, the filtrate was acidified again and the solid product was collected by filtration to give 5.2g of product in 86.7% yield.1H NMR:1.82(m,6H)；1.98(m,6H)；2.5(s,3H)；8.13(s,2H)；8.31(s,1H)；13.25(s,2H)。
And step 3: synthesis of 5- (1-adamantyl) -isophthaloyl dichloride
A500 mL dry flask was charged with 3g of 5- (1-adamantyl) -isophthalic acid, 10mL of thionyl chloride and 0.10mL of DMF, and reacted under reflux for 12 h. After the reaction was completed, the solvent was removed by rotary evaporation. The crude product was recrystallized from a dichloromethane/petroleum ether mixed solvent to give the product as a white solid with a yield of 85%.1H NMR:1.82(m,6H)；1.98(m,6H)；2.5(s,3H)；8.39(s,2H)；8.72(s,1H)。
And 4, step 4: synthesis of polyaramid containing adamantyl group
A250 mL dry flask was charged with p-phenylenediamine 1.08g and 50mL of NMP-LiCl solution and stirred at 0 deg.C until completely dissolved. The solution was left at room temperature and 3.37g of 5- (1-adamantyl) -isophthaloyl chloride was added. And mixing and stirring the reaction liquid for half an hour, and then heating to 60 ℃ for continuous reaction for 4 hours. And after the reaction is finished, dropwise adding the reaction liquid into hot water at the temperature of 90-100 ℃, stirring for 2h, filtering, dissolving the obtained solid product in NMP again, dropwise adding the solid product into a methanol solution again, stirring for 2h, filtering, washing the product with acetone, and drying to obtain the polyaramide material containing the adamantyl groups shown in the formula II. The polymer has GPC results as shown in fig. 2, which shows a single peak indicating successful preparation of the resulting polymer with good dispersibility.
Example 2, formula II polyaramid thermal stability test
For the polyaramid sample of formula II prepared in example 1, thermal stability was tested using a thermogravimetric analyzer (TGA) and the results are shown in fig. 3. The 5% thermogravimetric temperatures in nitrogen were 432 ℃ respectively. The polymer had a char yield of 32% at 800 ℃ in a nitrogen atmosphere, and was excellent in thermal stability.
Example 3 formula II polyaramid dielectric Performance testing
For the polyaramid sample of formula II prepared in example 1, its dielectric properties were tested using a broadband dielectric spectroscopy measurement system and the results are shown in fig. 4. As shown in FIG. 4, the dielectric constant of PAA was 2.75 at 1MHz (in contrast, PPTA, a para-aramid, has a dielectric constant of 7 and PMIA, a meta-aramid, has a dielectric constant of 4-5), demonstrating that the incorporation of adamantane can indeed reduce the dielectric constant. However, a dielectric loss of 0.062 (in contrast, a dielectric loss of 0.03 in PPTA, i.e., para-aramid, and a dielectric loss of 0.04 to 0.05 in PMIA, i.e., meta-aramid) is required), and further improvement is desired.
Example 4 mechanical Property testing of polyaramids of formula II
For the polyaramid sample of formula II prepared in example 1, the tensile properties of the film sample were tested using a universal tester, and the test results are shown in fig. 5. The Young modulus of the polyaramide is calculated to be 625MPa by analyzing the stress-strain curve, which shows that the polyaramide has excellent deformation resistance.
Example 5, formula II polyaramid solubility Performance test
A sample of 5.00mg of the polyaramid of the formula II prepared in example 1 was taken, and 0.5mL of each of different kinds of solvents was added thereto to test the solubility thereof. The results demonstrate that the polyaramids are soluble in partially strongly polar solvents such as: n-methyl pyrrolidone, dimethyl sulfoxide, N '-dimethyl formamide and N, N' -dimethyl acetamide, and has certain flow casting processing performance. But the paint is basically insoluble in common organic solvents such as toluene, tetrahydrofuran, chloroform and the like, and can resist solvent corrosion to a certain degree.
Claims (8)
1. A polyaramid material consisting of comonomer units of formula I:
wherein Ar is1Is selected from
One or more of; ar (Ar)2Is selected from
One or more of; n is an integer of 50 to 1000.
2. The method for producing the polyaramid material according to claim 1, wherein the method comprises the step of introducing ClOC-Ar under ice bath conditions1-COCl and H2N-Ar2-NH2Dissolving in a polar organic solvent for prepolymerization, removing the ice bath, continuing to react for a period of time at 20-60 ℃, finally precipitating the reaction solution in methanol or ethanol, and washing the precipitate to remove salts to obtain the polyaramide material.
3. The method according to claim 2, wherein the prepolymerization time is 30 to 60 minutes.
4. The method of claim 2, wherein the polar organic solvent is selected from one or more of the following solvents: n-methylpyrrolidone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, LiCl-containing N-methylpyrrolidone or dimethylformamide salt solutions.
5. The method according to claim 4, wherein the LiCl-containing N-methylpyrrolidone or dimethylformamide salt solution has a LiCl concentration of 1 to 8% by mass.
6. The method according to claim 2, wherein the reaction is carried out at 20 to 60 ℃ for 0.5 to 48 hours after the prepolymerization.
7. The preparation method of claim 2, wherein after the reaction at 20-60 ℃, the reaction solution is dripped into water at 90-100 ℃ for precipitation, the salt is removed, the solution is dissolved by a good solvent and then dripped into methanol or ethanol for precipitation, and the polyaramid material is obtained after filtration and drying.
8. The use of the polyaramid material of claim 1 in the preparation of dielectric insulating layer materials, communication antenna cladding materials, 5G base station cladding and protective materials.
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