CN116675852A - Novel copolyamide containing nylon 1 chain segment and having dielectric function and preparation method thereof - Google Patents
Novel copolyamide containing nylon 1 chain segment and having dielectric function and preparation method thereof Download PDFInfo
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- CN116675852A CN116675852A CN202310663227.3A CN202310663227A CN116675852A CN 116675852 A CN116675852 A CN 116675852A CN 202310663227 A CN202310663227 A CN 202310663227A CN 116675852 A CN116675852 A CN 116675852A
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- 239000004677 Nylon Substances 0.000 title claims abstract description 123
- 229920001778 nylon Polymers 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004952 Polyamide Substances 0.000 claims abstract description 44
- 229920002647 polyamide Polymers 0.000 claims abstract description 44
- 150000003839 salts Chemical class 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 33
- -1 piperazine-dodecanedioic acid salt Chemical class 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- 239000004246 zinc acetate Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 3
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 29
- 238000005303 weighing Methods 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000001816 cooling Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 230000005501 phase interface Effects 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000001257 hydrogen Chemical group 0.000 description 2
- 229910052739 hydrogen Chemical group 0.000 description 2
- 150000004885 piperazines Chemical class 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Materials Engineering (AREA)
- Polyamides (AREA)
Abstract
The invention belongs to the technical field of synthesis of all-organic polymer dielectric films, and particularly relates to novel copolyamide containing nylon 1 chain segments and having a dielectric function and a preparation method thereof, wherein the preparation method of the novel dielectric polyamide film containing the nylon 1 chain segments comprises the following steps: the method comprises the steps of synthesizing nylon 1 with different polymerization degrees, forming salts with piperazine by succinic anhydride end-capped nylon 1 and end-capped products (PA 1 diacid for short), performing copolycondensation reaction of piperazine-PA1 diacid salt and piperazine-dodecanedioic acid salt, hot-press molding and the like. In the invention, piperazine-PA1 diacid salt and piperazine-dodecanedioic acid salt are copolycondensed at high temperature and high pressure, the high dielectric constant of a nylon 1 chain segment and the unique low dielectric loss of piperazine nylon are combined, nylon 1 is used as a dielectric functional chain segment to be embedded into a piperazine nylon matrix, and the novel dielectric polyamide film containing the nylon 1 chain segment is directly prepared through simple hot press molding.
Description
Technical Field
The invention belongs to the technical field of synthesis of all-organic polymer dielectric films, and particularly relates to novel copolyamide containing nylon 1 chain segments and having a dielectric function and a preparation method thereof.
Background
The polymer film capacitor is widely applied to the fields of electric automobiles, pulse power systems, smart grids and the like due to the advantages of easiness in processing, high voltage resistance and the like. Biaxially oriented polypropylene (BOPP) has been the most popular polymer dielectric for recent decades due to its low dielectric loss (tan delta < 0.003) and high breakdown strength (> 500 MV/m). However, its low dielectric constant (1.8-2.2) results in its low energy storage density, which severely hampers its application in advanced pulse electronics. Therefore, new generation polymer film capacitor applications are in urgent need for dielectric polymers with high dielectric constants.
Nylon 1, i.e. PAI, also known as polycarbonyl urea, has the chemical structureThe nylon material having the highest dielectric constant is theoretically the nylon material having the highest density of amide groups and hydrogen bond density in polyamides. The maximum dielectric constant can reach 30-40@ (10) 2 -10 5 ). However, nylon 1 is generally a rigid powder that is difficult to process into a film due to its high molecular chain rigidity and strong intermolecular forces, which greatly limits its application as a dielectric functional material. The inventor tries to directly add nylon 1 as a dielectric function filler into PVDF and nylon 11 matrixes, and the dielectric constants of the prepared composite dielectric medium are obviously improved. However, the introduction of nylon 1 also causes a large number of phase interfaces, which results in a large dielectric loss of the composite dielectric, and is difficult to be practically used.
No similar method for solving the above problems has been reported in the literature. By means of the copolymerization, it is possible to combine the corresponding excellent properties of the individual structural units and without this leading to complex phase interfaces in similar composites. Therefore, nylon 1 is introduced as a dielectric functional segment into a molecular chain of a polymer having low dielectric loss and excellent mechanical properties, and it is expected to combine the high dielectric constant of nylon 1 with the low dielectric loss of other polymers and excellent film forming properties.
The invention selects nylon Long Paiqin-12 with low dielectric loss and excellent mechanical property as a basic polymer, nylon 1 is used as a functional structural unit, and the novel dielectric polyamide film containing nylon 1 chain segments is prepared by capping nylon 1, salifying with piperazine, copolymerizing with piperazine-dodecanedioic acid salt and simply combining with hot pressing or extrusion molding. The comprehensive performance of the obtained dielectric film can be easily adjusted by selecting nylon 1 with different polymerization degrees and adjusting the mole content of nylon 1 chain segments. The polyamide film prepared by the method has high dielectric constant, low dielectric loss and excellent mechanical toughness, and provides a new thought for chemical structural design of dielectric polymers.
Disclosure of Invention
The invention provides a method for preparing a novel dielectric polyamide film containing nylon 1 chain segments, which solves the problems that the dielectric constant of the existing polymer dielectric medium is low and the nylon 1 reported at present is difficult to thin. According to the invention, nylon 1 chain segments with different lengths or molar contents are introduced into the molecular chain of nylon piperazine-12, and the combination of the high dielectric constant of the nylon 1 chain segments and the low dielectric loss and excellent mechanical properties of piperazine long-chain diacid nylon greatly promotes the application of nylon 1 as a novel dielectric functional material in the field of film capacitors, and provides a new thought and method for the chemical structural design of dielectric polymers.
In order to achieve the above purpose, the present invention provides the following technical solutions: a novel copolyamide containing nylon 1 chain segment and having dielectric function has the structural formula:
wherein n=3-8, the nylon 1 segment imparts a high dielectric constant to the polyamide film; piperazine polyamide segments impart low dielectric loss to the polyamide film, and piperazine12 segments provide excellent mechanical flexibility.
Preferably, the chemical structure of the catalyst is strong in adjustability; nylon 1 chain segments with different polymerization degrees can be selected, and the molar content of the nylon 1 chain segments can be adjusted; polyamides and films thereof with different dielectric properties are prepared by different chemical structures and compositions.
Preferably, a method of preparation comprises the steps of:
step 1: synthesizing nylon 1 by adopting a urea self-polycondensation method; zinc acetate is used as a catalyst, polycondensation reaction is carried out in nitrogen atmosphere, and then heat treatment is carried out; different heat treatment conditions can obtain nylon 1 with different polymerization degrees; wherein the stirring rotation speed is set to be 100-300r/min;
step 2: succinic anhydride and nylon 1 prepared in the step 1 are mixed according to a molar ratio of 3:1, carrying out end-capping reaction in an autoclave; washing the product with dichloromethane, suction filtering, extracting the obtained filter residue with ethyl acetate to obtain nylon 1 (hereinafter referred to as "PA1 diacid") with carboxyl groups at both ends; the chemical structure is as follows:
step 3: and (2) respectively mixing the end-capped products PA1 diacid and dodecanedioic acid prepared in the step (2) with piperazine according to a molar ratio of 1:1.05, carrying out salt forming reaction to obtain piperazine-PA1 diacid salt and piperazine-dodecanedioic acid salt containing nylon 1 chain segments;
step 4: adding piperazine-PA1 diacid salt and piperazine-dodecanedioic acid salt into an autoclave according to different set molar ratios for copolymerization reaction; the reaction process is that pre-polymerization is carried out firstly, and then tackifying is carried out, so that copolyamide with high molecular weight is obtained; wherein the stirring rotation speed of the autoclave is set to be 100-300r/min;
step 5: and (3) carrying out hot pressing or extrusion molding on the copolyamide obtained in the step (4) to obtain the novel dielectric polyamide film containing the nylon 1 chain segment, wherein the thickness of the film is controlled to be 50-120 mu m.
Preferably, in the step 1, the reaction temperature of the urea self-polycondensation reaction is 150-160 ℃, the reaction time is 16-30 hours, and nitrogen protection is adopted in the reaction process; zinc acetate is used as the catalyst in the reaction process. The catalyst can also be alkaline catalyst such as potassium carbonate, potassium oxide, sodium carbonate, etc.
Preferably, in the step 1, the heat treatment temperature is 160-220 ℃, the heat treatment time is 4-12 hours, and the heat treatment process takes 3-5MPa carbon dioxide as atmosphere.
Preferably, the nylon 1 produced by the polycondensation reaction in the step 1 has the structure:
wherein n represents the polymerization degree of nylon 1, and nylon 1 having different polymerization degrees is synthesized specifically by controlling the polycondensation reaction and the heat treatment time.
Preferably, the reaction temperature of the end capping reaction in the step 2 is 110-130 ℃ and the reaction time is 8-24 hours; the excess succinic anhydride was washed with dichloromethane and the product mixture was purified by extraction with ethyl acetate.
Preferably, the salifying reaction in the step 3 uses water as a solvent, the reaction temperature is 50-80 ℃, and the pH value is controlled to be 7.2-7.4 after the reaction is finished; concentrating the salt solution by reduced pressure distillation, precipitating with ethanol, and drying to obtain nylon dry salt.
Preferably, the piperazine-PA1 diacid salt and piperazine-dodecanedioic acid salt containing the nylon 1 chain segment prepared by the salification reaction in the step 3 are respectively:
preferably, in the step 4, the piperazine-PA1 diacid salt and the piperazine-dodecanedioic acid salt containing the nylon 1 chain segments obtained in the step 3 are added into a polymerization reaction kettle together for copolymerization reaction, water, a catalyst, an antioxidant and the like are also added, the mass of the added water is 1/2 of the total mass of the nylon salt, and the mass of the added catalyst and antioxidant is 0.3-0.5 wt% of the total mass of the nylon salt respectively.
Preferably, in the step 4, the reaction temperature of the prepolymerization is 160-190 ℃, the reaction time is 2 hours, and the reaction pressure is controlled below the saturated vapor pressure of water, specifically 0.3-0.5MPa; the tackifying reaction temperature is 230-250 ℃, and the reaction is carried out for 2 hours at constant pressure; and then a circulating water type vacuum pump is adopted for vacuumizing, the vacuum degree is 0.09MPa, and the reaction time is 2 hours.
Preferably, in the step 5, the hot press molding process of the nylon film is that plasticizing is firstly carried out for 10 minutes at 210-230 ℃; hot-pressing at 210-230 deg.c for 5 min at 10MPa; finally cold pressing for 3 minutes at room temperature, wherein the pressure is 10MPa.
The invention has the beneficial effects that: the nylon 1 is introduced into a polymer molecular chain as a novel dielectric functional chain segment by adopting anhydride end capping, salifying and copolymerization reaction. Compared with the prior reported method for compounding nylon 1 as a dielectric functional filler with a polymer matrix, the method eliminates a large amount of phase interface problems in a composite dielectric medium, and the prepared dielectric film has more excellent comprehensive performance, thereby greatly promoting the application of nylon 1 in a film capacitor.
The invention selects piperazine12 nylon which does not contain intermolecular hydrogen bonds as a main chain, and has the advantages of low dielectric loss, excellent mechanical toughness, good film forming property and the like. The novel dielectric polyamide film containing the nylon 1 chain segment has great practical value by combining the high dielectric constant of nylon 1 with the low dielectric loss of piperazine nylon and excellent film forming property. The nylon 1 chain segment with proper content also improves the Young modulus, breaking strength and breakdown strength of the copolymer.
Compared with the prior reported dielectric polypropylene or PVDF, the novel dielectric polyamide prepared by the invention has good chemical structure adjustability, not only can adjust the polymerization degree of nylon 1, but also can adjust the content of nylon 1 chain segments, and provides a new thought for the chemical structure design of dielectric polymers.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of a novel dielectric polyamide film comprising a nylon 1 segment in examples 1,2, and 3.
FIG. 2 is a DSC of a novel dielectric polyamide film containing nylon 1 segments in example 3.
FIG. 3 shows nuclear magnetic resonance spectra of novel dielectric polyamides containing nylon 1 segments in examples 1,2 and 3.
FIG. 4 shows XRD patterns of novel dielectric polyamide films containing nylon 1 segments in examples 1,2 and 3.
FIG. 5 is a graph showing the variation of the dielectric constant with frequency of the novel dielectric polyamide film having nylon 1 segment in examples 1,2 and 3.
FIG. 6 is a graph showing the dielectric loss of the novel dielectric polyamide films containing nylon 1 segments as a function of frequency in examples 1,2 and 3.
FIG. 7 is a graph showing the dielectric properties of the novel dielectric polyamide film having nylon 1 segments prepared in example 3 compared with that of the homopolymerized nylon piperazine 12.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
As shown in fig. 1, 3, 4, 5 and 6, a novel dielectric polyamide film (abbreviated as Piperazine-PA 1) containing nylon 1 chain segments a 7.5%) of the preparation method:
step 1: nylon 1 synthesis. Weighing proper amount of urea and 5wt% zinc acetate catalyst into a round bottom flask, and using constant-rate high-purity N 2 And (3) carrying out constant-temperature reaction for 18h in an oil bath kettle at 155-160 ℃ under the protection, after the reaction is finished, closing heating, cooling to room temperature, taking out the product, and then transferring the product into an autoclave at 160 ℃ for heat treatment for 4h, wherein the atmosphere of the autoclave is 3.5MPa of carbon dioxide gas. The crude product was a white, lumpy solid. Washing off residual urea and catalyst with deionized water to obtain white powdery PA1 (polymerization degree about 3.7, PA1 for short) a )。
Step 2: PA1 a Is carboxyl terminated. Weighing PA1 according to a molar ratio of 1:3 a And succinic anhydride are uniformly mixed and poured into a 1000mL three-neck flask, and the flask is sealed, vacuumized and replaced by nitrogen for three times. Setting the temperature of an oil bath pot to be 110 ℃ and the rotating speed to be 200r/min, preserving heat and reacting for 12 hours, pouring the reactant into methylene dichloride while the reactant is hot to precipitate, removing excessive succinic anhydride, extracting by ethyl acetate, and obtaining the PA1 with carboxyl at both ends a A diacid.
Step 3: piperazine-PA1 a Preparation of diacid salt and piperazine-dodecanedioic acid salt. And (2) respectively weighing the PA1 obtained in the step (2) proportionally a The diacid or dodecanedioic acid is poured into deionized water to be fully stirred and dissolved, and is complexed with piperazine into salt at the constant temperature of 55 ℃ in an oil bath. And monitoring the PH value in real time in the process of gradually adding piperazine to judge the reaction end point. When the pH in the system reached a value in the range of 7.2 to 7.3 and there was no change for half an hour, the heating was terminated. When the temperature of the system was lowered to room temperature, stirring was stopped. The salt solution was filtered again with a quick filter paper and buchner funnel under reduced pressure, and the clear salt solution was taken and placed in a flask in a water bath at 60 ℃ for rotary distillation. All water was spin evaporated to dryness and then poured into absolute ethanol for transfer and the product was washed three times with absolute ethanol repeatedly after filtration using a quick filter paper and buchner funnel. Drying in an oven at 80 ℃ for 3 hours to obtain piperazine-PA1 a Diacid salts and piperazine-dodecanedioic acid salts.
Step 4: and (3) copolymerization reaction. According to piperazine-PA1 a The molar ratio of diacid salt to piperazine-dodecanedioic acid salt was 7.5:92.5 weighing 20g of the salt prepared in the step 3, 10g of deionized water, 0.015g of sodium hypophosphite and 0.045g of antioxidant 445, adding the total salt into a 100ml tetrafluoroethylene beaker, putting the beaker into a micro autoclave, sealing, vacuumizing, introducing nitrogen and circulating for 5 times. Stirring was started and the rotational speed was set at 300r/min. Heating to 180 ℃, and reacting for 2 hours at constant pressure. Opening the air outlet, discharging the water vapor in the reaction system to normal pressure, and closing the air outlet; heating upConstant pressure reaction for 2 hours at 240 ℃; vacuumizing a circulating water pump, keeping the temperature at 240 ℃ and reacting for 2 hours; the rotary vane vacuum pump is used for vacuumizing, the constant temperature is 240 ℃, and the reaction is carried out for 2 hours. And (3) closing heating, cooling the reaction system to room temperature, and taking out the product, wherein the product is light yellow blocky high polymer copolyamide.
Step 5: preparation of novel dielectric polyamide films containing nylon 1 segments. Plasticizing the copolyamide obtained in the step 4 at 220 ℃ for 10 minutes; hot-pressing at 220 deg.c for 5 min at 10MPa; finally cold pressing for 3 minutes at room temperature, wherein the pressure is 10MPa, so that the novel dielectric polyamide film containing nylon 1 chain segments is prepared, and the thickness of the film is controlled to be 80+/-20 mu m.
According to the same synthesis process and auxiliary agent formula, only Piperazine-dodecanedioic acid salt is used for synthesizing nylon Piperazine12 homopolymer (Piperazine 12 for short) for improving the dielectric property of the copolyamide containing nylon 1 chain segment.
The Fourier infrared spectrum (FTIR) and Nuclear Magnetic Resonance (NMR) of the product are shown in figures 1 and 3, respectively. As can be seen from the figure, copolyamides containing nylon 1 segments have been successfully synthesized. Fig. 5 and 6 show that the resultant copolyamide has excellent dielectric properties.
Example 2
As shown in fig. 1, 3, 4, 5 and 6, a novel dielectric polyamide film (abbreviated as Piperazine-PA 1) containing nylon 1 chain segments a 11%) of the preparation method:
step 1: nylon 1 synthesis. Weighing proper amount of urea and 5wt% zinc acetate catalyst into a round bottom flask, and using constant-rate high-purity N 2 And (3) carrying out constant-temperature reaction for 18h in an oil bath kettle at 155-160 ℃ under the protection, after the reaction is finished, closing heating, cooling to room temperature, taking out a product, and then transferring the product into an autoclave at 160 ℃ for heat treatment for 4h, wherein the atmosphere of the autoclave is carbon dioxide gas at 3.5 MPa. The crude product was a white, lumpy solid. Washing off residual urea and catalyst with deionized water to obtain white powdery PA1 (polymerization degree about 3.7, PA1 for short) a )。
Step 2: PA1 a Is carboxyl terminated. Weighing according to a molar ratio of 1:3PA1 a And succinic anhydride are uniformly mixed and poured into a 1000mL three-neck flask, and the flask is sealed, vacuumized and replaced by nitrogen for three times. Setting the temperature of an oil bath pot to be 110 ℃ and the rotating speed to be 200r/min, preserving heat and reacting for 12 hours, pouring the reactant into methylene dichloride while the reactant is hot to precipitate, removing excessive succinic anhydride, extracting by ethyl acetate, and obtaining the PA1 with carboxyl at both ends a A diacid.
Step 3: piperazine-PA1 a Preparation of diacid salt and piperazine-dodecanedioic acid salt. And (2) respectively weighing the PA1 obtained in the step (2) proportionally a The diacid or dodecanedioic acid is poured into deionized water to be fully stirred and dissolved, and is complexed with piperazine into salt at the constant temperature of 55 ℃ in an oil bath. And monitoring the PH value in real time in the process of gradually adding piperazine to judge the reaction end point. When the pH in the system reached a value in the range of 7.2 to 7.3 and there was no change for half an hour, the heating was terminated. When the temperature of the system was lowered to room temperature, stirring was stopped. The salt solution was filtered again with a quick filter paper and buchner funnel under reduced pressure, and the clear salt solution was taken and placed in a flask in a water bath at 60 ℃ for rotary distillation. All water was spin evaporated to dryness and then poured into absolute ethanol for transfer and the product was washed three times with absolute ethanol repeatedly after filtration using a quick filter paper and buchner funnel. Drying in an oven at 80 ℃ for 3 hours to obtain piperazine-PA1 a Diacid salts and piperazine-dodecanedioic acid salts.
Step 4: copolymerization of piperazine-PA1 a The molar ratio of diacid salt to piperazine-dodecanedioic acid salt is 11:89 weighing the total 20g of salt prepared in the step 3, 30g of deionized water, 0.015g of sodium hypophosphite and 0.045g of antioxidant 445, adding the total into a 100ml tetrafluoroethylene beaker, putting the beaker into a miniature autoclave, sealing, vacuumizing, introducing nitrogen and circulating for 5 times. Stirring was started and the rotational speed was set at 300r/min. Heating to 180 ℃, and reacting for 2 hours at constant pressure. Opening the air outlet, discharging the water vapor in the reaction system to normal pressure, and closing the air outlet; heating to 245 ℃, and reacting for 2 hours at constant pressure; vacuumizing a circulating water pump, keeping the temperature at 245 ℃ and reacting for 2 hours; the rotary vane vacuum pump is used for vacuumizing, the constant temperature is 245 ℃, and the reaction is carried out for 2 hours. And (3) closing heating, cooling the reaction system to room temperature, and taking out the product, wherein the product is light yellow blocky high polymer copolyamide.
Step 5: preparing a novel dielectric polyamide film containing nylon 1 chain segments, and plasticizing the copolyamide obtained in the step 4 at 220 ℃ for 10 minutes; hot-pressing at 220 deg.c for 5 min at 10MPa; finally cold pressing for 3 minutes at room temperature, wherein the pressure is 10MPa, so that the novel dielectric polyamide film containing nylon 1 chain segments is prepared, and the thickness of the film is controlled to be 80+/-20 mu m.
According to the same synthesis process and auxiliary agent formula, only Piperazine-dodecanedioic acid salt is used for synthesizing nylon Piperazine12 homopolymer (Piperazine 12 for short) for improving the dielectric property of the copolyamide containing nylon 1 chain segment.
The Fourier infrared spectrum (FTIR) and Nuclear Magnetic Resonance (NMR) of the product are shown in figures 1 and 3, respectively. As can be seen from the figure, copolyamides containing nylon 1 segments have been successfully synthesized. FIG. 5 and FIG. 6 show that the prepared copolyamide film has excellent dielectric properties.
Example 3
As shown in fig. 1,2,3, 4, 5, 6 and 7, a novel dielectric polyamide film (abbreviated as Piperazine12-PA 1) containing nylon 1 chain segments a 15%) of the preparation method:
step 1: nylon 1 synthesis. Weighing proper amount of urea and 5wt% zinc acetate catalyst into a round bottom flask, and using constant-rate high-purity N 2 And (3) carrying out constant-temperature reaction for 18h in an oil bath kettle at 155-160 ℃ under the protection, after the reaction is finished, closing heating, cooling to room temperature, taking out a product, and then transferring the product into an autoclave at 160 ℃ for heat treatment for 4h, wherein the atmosphere of the autoclave is carbon dioxide gas at 3.5 MPa. The crude product was a white, lumpy solid. Washing off residual urea and catalyst with deionized water to obtain white powdery PA1 (polymerization degree about 3.7, PA1 for short) a )。
Step 2: PA1 a Is carboxyl terminated. Weighing PA1 according to a molar ratio of 1:3 a And succinic anhydride are uniformly mixed and poured into a 1000mL three-neck flask, and the flask is sealed, vacuumized and replaced by nitrogen for three times. Setting the temperature of an oil bath pot to be 110 ℃ and the rotating speed to be 200r/min, preserving the heat and reacting for 12 hours, pouring the reactant into dichloromethane while the reactant is hot for precipitation,removing excessive succinic anhydride, extracting with ethyl acetate to obtain PA1 with carboxyl groups at both ends a A diacid.
Step 3: piperazine-PA1 a Preparation of diacid salt and piperazine-dodecanedioic acid salt. And (2) respectively weighing the PA1 obtained in the step (2) proportionally a The diacid or dodecanedioic acid is poured into deionized water to be fully stirred and dissolved, and is complexed with piperazine into salt at the constant temperature of 55 ℃ in an oil bath. And monitoring the PH value in real time in the process of gradually adding piperazine to judge the reaction end point. When the pH in the system reached a value in the range of 7.2 to 7.3 and there was no change for half an hour, the heating was terminated. When the temperature of the system was lowered to room temperature, stirring was stopped. The salt solution was filtered again with a quick filter paper and buchner funnel under reduced pressure, and the clear salt solution was taken and placed in a flask in a water bath at 60 ℃ for rotary distillation. All water was spin evaporated to dryness and then poured into absolute ethanol for transfer and the product was washed three times with absolute ethanol repeatedly after filtration using a quick filter paper and buchner funnel. Drying in an oven at 80 ℃ for 3 hours to obtain piperazine-PA1 a Diacid salts and piperazine-dodecanedioic acid salts.
Step 4: and (3) copolymerization reaction. The molar ratio of piperazine salt containing nylon 1 chain segment to piperazine-dodecanedioic acid salt is 15:85 weighing the total 20g of salt prepared in the step 3, 30g of deionized water, 0.015g of sodium hypophosphite and 0.045g of antioxidant 445, adding the total into a 100ml tetrafluoroethylene beaker, putting the beaker into a miniature autoclave, sealing, vacuumizing, introducing nitrogen and circulating for 5 times. Stirring was started and the rotational speed was set at 300r/min. Heating to 180 ℃, and reacting for 2 hours at constant pressure. Opening the air outlet, discharging the water vapor in the reaction system to normal pressure, and closing the air outlet; heating to 250 ℃, and reacting for 2 hours at constant pressure; vacuumizing a circulating water pump, keeping the temperature at 250 ℃ and reacting for 2 hours; the rotary vane vacuum pump is used for vacuumizing, the constant temperature is 250 ℃, and the reaction is carried out for 2 hours. And (3) closing heating, cooling the reaction system to room temperature, and taking out the product, wherein the product is light yellow blocky high polymer copolyamide.
Step 5: preparation of novel dielectric polyamide films containing nylon 1 segments. Plasticizing the copolyamide obtained in the step 4 at 220 ℃ for 10 minutes; hot-pressing at 220 deg.c for 5 min at 10MPa; finally cold pressing for 3 minutes at room temperature, wherein the pressure is 10MPa, so that the novel dielectric polyamide film containing nylon 1 chain segments is prepared, and the thickness of the film is controlled to be 80+/-20 mu m.
According to the same synthesis process and formula, only Piperazine-dodecanedioic acid salt is used for synthesizing nylon Piperazine12 homopolymer (Piperazine 12 for short) for improving the dielectric property of the copolyamide containing nylon 1 chain segment.
The Fourier infrared spectrum (FTIR) and Nuclear Magnetic Resonance (NMR) of the product are shown in figures 1 and 3, respectively. As can be seen from the figure, copolyamides containing nylon 1 segments have been successfully synthesized. Fig. 5, 6 and 7 show that the resultant copolyamide has excellent dielectric properties. The dielectric constant of the copolyamide Piperazine12-PA1 is improved by nearly 2 times compared with that of the matrix nylon Piperazine12, and the dielectric loss is kept unchanged.
Example 4
Novel dielectric polyamide film (Piperazine 12-PA1 for short) containing nylon 1 chain segment b 12%) of the preparation method:
step 1: nylon 1 synthesis. Weighing proper amount of urea and 5wt% zinc acetate catalyst into a round bottom flask, and using constant-rate high-purity N 2 Under protection, carrying out constant temperature reaction for 18h in an oil bath pot at 155-160 ℃, after the reaction is finished, closing heating, cooling to room temperature, taking out the product, transferring to an autoclave at 160 ℃ for heat treatment for 2h, heat treatment at 170 ℃ for 4h, and heat treatment at 180 ℃ for 2h, wherein the atmosphere of the autoclave is carbon dioxide gas at 4.0-4.5 MPa. The crude product was a white, lumpy solid. Washing off residual urea and catalyst with deionized water to obtain white powdery PA1 (polymerization degree about 4.6, PA1 for short) b )。
Step 2: PA1 b Is carboxyl terminated. Weighing PA1 according to a molar ratio of 1:3 b And succinic anhydride are uniformly mixed and poured into a 1000mL three-neck flask, and the flask is sealed, vacuumized and replaced by nitrogen for three times. Setting the temperature of an oil bath pot to be 110 ℃ and the rotating speed to be 200r/min, preserving heat and reacting for 12 hours, pouring the reactant into methylene dichloride while the reactant is hot to precipitate, removing excessive succinic anhydride, extracting by ethyl acetate, and obtaining the PA1 with carboxyl at both ends b A diacid.
Step 3: piperazine sheetoxazine-PA 1 b Preparation of diacid salt and piperazine-dodecanedioic acid salt. And (2) respectively weighing the PA1 obtained in the step (2) proportionally b The diacid or dodecanedioic acid is poured into deionized water to be fully stirred and dissolved, and is complexed with piperazine into salt at the constant temperature of 55 ℃ in an oil bath. And monitoring the PH value in real time in the process of gradually adding piperazine to judge the reaction end point. When the pH in the system reached a value in the range of 7.2 to 7.3 and there was no change for half an hour, the heating was terminated. When the temperature of the system was lowered to room temperature, stirring was stopped. The salt solution was filtered again with a quick filter paper and buchner funnel under reduced pressure, and the clear salt solution was taken and placed in a flask in a water bath at 60 ℃ for rotary distillation. All water was spin evaporated to dryness and then poured into absolute ethanol for transfer and the product was washed three times with absolute ethanol repeatedly after filtration using a quick filter paper and buchner funnel. Drying in an oven at 80 ℃ for 3 hours to obtain piperazine-PA1 b Diacid salts and piperazine-dodecanedioic acid salts.
Step 4: and (3) copolymerization reaction. According to piperazine-PA1 b The mole ratio of diacid salt and piperazine-dodecanedioic acid salt is 12:88 weighing the total 20g of salt prepared in the step 3, 30g of deionized water, 0.015g of sodium hypophosphite and 0.045g of antioxidant 445, adding the total into a 100ml tetrafluoroethylene beaker, putting the beaker into a miniature autoclave, sealing, vacuumizing, introducing nitrogen and circulating for 5 times. Stirring was started and the rotational speed was set at 300r/min. Heating to 180 ℃, and reacting for 2 hours at constant pressure. Opening the air outlet, discharging the water vapor in the reaction system to normal pressure, and closing the air outlet; heating to 250 ℃, and reacting for 2 hours at constant pressure; vacuumizing a circulating water pump, keeping the temperature at 250 ℃ and reacting for 2 hours; the rotary vane vacuum pump is used for vacuumizing, the constant temperature is 250 ℃, and the reaction is carried out for 2 hours. And (3) closing heating, cooling the reaction system to room temperature, and taking out the product, wherein the product is light yellow blocky high polymer copolyamide.
Step 5: preparation of novel dielectric polyamide films containing nylon 1 segments. Plasticizing the copolyamide obtained in the step 4 at 220 ℃ for 10 minutes; hot-pressing at 220 deg.c for 5 min at 10MPa; finally cold pressing for 3 minutes at room temperature, wherein the pressure is 10MPa, so that the novel dielectric polyamide film containing nylon 1 chain segments is prepared, and the thickness of the film is controlled to be 100+/-20 mu m.
The nylon 1 chain segment is preparedThe dielectric constant of the novel dielectric polyamide film is 6.4-6.8@ (10 2 -10 5 ) Dielectric loss of 0.002-0.003@ (10 2 -10 5 )。
Example 5
Novel dielectric polyamide film (Piperazine 12-PA1 for short) containing nylon 1 chain segment b 20%) of the preparation method:
step 1: nylon 1 synthesis. Weighing proper amount of urea and 5wt% zinc acetate catalyst into a round bottom flask, and using constant-rate high-purity N 2 Under protection, carrying out constant temperature reaction for 18h in an oil bath pot at 155-160 ℃, after the reaction is finished, closing heating, cooling to room temperature, taking out the product, transferring to an autoclave at 160 ℃ for heat treatment for 2h, heat treatment at 170 ℃ for 4h, and heat treatment at 180 ℃ for 2h, wherein the atmosphere of the autoclave is carbon dioxide gas at 4.0-4.5 MPa. The crude product was a white, lumpy solid. Washing off residual urea and catalyst with deionized water to obtain white powdery PA1 (polymerization degree about 4.6, PA1 for short) b )。
Step 2: PA1 b Is carboxyl terminated. Weighing PA1 according to a molar ratio of 1:3 b And succinic anhydride are uniformly mixed and poured into a 1000mL three-neck flask, and the flask is sealed, vacuumized and replaced by nitrogen for three times. Setting the temperature of an oil bath pot to be 110 ℃ and the rotating speed to be 200r/min, preserving heat and reacting for 12 hours, pouring the reactant into methylene dichloride while the reactant is hot to precipitate, removing excessive succinic anhydride, extracting by ethyl acetate, and obtaining the PA1 with carboxyl at both ends b A diacid.
Step 3: piperazine-PA1 b Preparation of diacid salt and piperazine-dodecanedioic acid salt. And (2) respectively weighing the PA1 obtained in the step (2) proportionally b The diacid or dodecanedioic acid is poured into deionized water to be fully stirred and dissolved, and is complexed with piperazine into salt at the constant temperature of 55 ℃ in an oil bath. And monitoring the PH value in real time in the process of gradually adding piperazine to judge the reaction end point. When the pH in the system reached a value in the range of 7.2 to 7.3 and there was no change for half an hour, the heating was terminated. When the temperature of the system was lowered to room temperature, stirring was stopped. The salt solution was filtered again with a quick filter paper and buchner funnel under reduced pressure, and the clear salt solution was taken and placed in a flask in a water bath at 60 ℃ for rotary distillation. Completely evaporating water by rotary evaporation, and pouring into anhydrousThe product was ethanol transferred and washed, filtered using a quick filter paper and buchner funnel and washed three times with anhydrous ethanol repeatedly. Drying in an oven at 80 ℃ for 3 hours to obtain piperazine-PA1 b Diacid salts and piperazine-dodecanedioic acid salts.
Step 4: and (3) copolymerization reaction. The molar ratio of piperazine salt containing nylon 1 chain segment to piperazine-dodecanedioic acid salt is 20:80 weighing 20g of the salt prepared in the step 3, 30g of deionized water, 0.015g of sodium hypophosphite and 0.045g of antioxidant 445, adding the total salt into a 100ml tetrafluoroethylene beaker, putting the beaker into a miniature autoclave, sealing, vacuumizing, introducing nitrogen and circulating for 5 times. Stirring was started and the rotational speed was set at 200r/min. Heating to 180 ℃, and reacting for 2 hours at constant pressure. Opening the air outlet, discharging the water vapor in the reaction system to normal pressure, and closing the air outlet; heating to 250 ℃, and reacting for 2 hours at constant pressure; vacuumizing a circulating water pump, keeping the temperature at 250 ℃ and reacting for 2 hours; the rotary vane vacuum pump is used for vacuumizing, the constant temperature is 250 ℃, and the reaction is carried out for 2 hours. And (3) closing heating, cooling the reaction system to room temperature, and taking out the product, wherein the product is light yellow blocky high polymer copolyamide.
Step 5: preparation of novel dielectric polyamide films containing nylon 1 segments. Plasticizing the copolyamide obtained in the step 4 at 230 ℃ for 10 minutes; hot-pressing at 230 ℃ for 5 minutes under the pressure of 10MPa; finally cold pressing for 3 minutes at room temperature, wherein the pressure is 10MPa, so that the novel dielectric polyamide film containing nylon 1 chain segments is prepared, and the thickness of the film is controlled to be 100+/-20 mu m.
The dielectric constant of the novel dielectric polyamide film containing nylon 1 chain segment is 7.2-7.6@ (10 2 -10 5 ) Dielectric loss of 0.002-0.003@ (10 2 -10 5 )。
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (12)
1. A novel copolyamide with dielectric function containing nylon 1 chain segment, which is characterized in that: the structural formula is as follows:
wherein n=3-8, the nylon 1 segment imparts a high dielectric constant to the polyamide film; the piperazine polyamide segment imparts low dielectric loss to the polyamide film, and the piperazine12 segment provides excellent mechanical flexibility.
2. A novel copolyamide with dielectric function containing nylon 1 chain segment, which is characterized in that: the adjustability of the chemical structure is strong; nylon 1 chain segments with different polymerization degrees can be selected, and the molar content of the nylon 1 chain segments can be adjusted; the polyamide and the film thereof with different dielectric properties are prepared by the oligomeric nylon 1 with different polymerization degrees and the content.
3. A process for preparing the novel dielectric polyamide film comprising nylon 1 segments of claim 1, characterized in that: the method comprises the following steps:
step 1: synthesizing nylon 1 by adopting a urea self-polycondensation method; zinc acetate is used as a catalyst, polycondensation reaction is carried out in nitrogen atmosphere, and then heat treatment is carried out; the nylon 1 with different polymerization degrees can be obtained by different heat treatment conditions, wherein the stirring rotation speed is set to be 100-300r/min;
step 2: succinic anhydride and nylon 1 prepared in the step 1 are mixed according to a molar ratio of 3:1, carrying out end-capping reaction in an autoclave; washing the product with dichloromethane and extracting with ethyl acetate to obtain nylon 1 with carboxyl groups at two ends, namely: PA1 diacid, its chemical structure is:
step 3: piperazine and PA1 diacid and dodecanedioic acid prepared in the step 2 are respectively mixed according to the mol ratio of 1.05:1, carrying out salt forming reaction to obtain piperazine-PA1 diacid salt and piperazine-dodecanedioic acid salt;
step 4: piperazine-PA1 diacid salt and piperazine-dodecanedioic acid salt are added into an autoclave according to a certain proportion to carry out copolymerization reaction; the reaction process is that pre-polymerization is carried out firstly, and then tackifying is carried out, so that copolyamide with high molecular weight is obtained; wherein the stirring rotation speed of the autoclave is set to be 100-300r/min;
step 5: and (3) carrying out hot press molding on the copolyamide obtained in the step (4) to obtain the novel dielectric polyamide film containing nylon 1 chain segments, wherein the thickness of the film is controlled to be 50-120 mu m.
4. A method of preparation according to claim 3, characterized in that: in the step 1, the reaction temperature of the urea self-polycondensation reaction is 150-160 ℃, the reaction time is 16-30 hours, and nitrogen protection is adopted in the reaction process; the alkaline catalyst in the reaction process can be any one of zinc acetate, potassium carbonate, potassium oxide and sodium carbonate.
5. A method of preparation according to claim 3, characterized in that: in the step 1, the heat treatment temperature is 160-220 ℃, the heat treatment time is 4-12 hours, and the heat treatment process takes 3-5MPa carbon dioxide as atmosphere.
6. A method of preparation according to claim 3, characterized in that: the nylon 1 produced by the polycondensation reaction in the step 1 has the structure that:
wherein n represents the polymerization degree of nylon 1, and specifically nylon 1 having different polymerization degrees is synthesized by controlling the heat treatment temperature and time.
7. A method of preparation according to claim 3, characterized in that: the reaction temperature of the end capping reaction in the step 2 is 110-130 ℃ and the reaction time is 8-24 hours; the excess succinic anhydride was washed with dichloromethane and the resulting product mixture was extracted with ethyl acetate and purified.
8. A method of preparation according to claim 3, characterized in that: the salification reaction in the step 3 takes water as a solvent, the reaction temperature is 50-80 ℃, and the pH value is controlled to be 7.2-7.3 after the reaction is finished; concentrating the salt solution by reduced pressure distillation, precipitating with ethanol, and drying to obtain nylon dry salt.
9. A method of preparation according to claim 3, characterized in that: the piperazine-PA1 diacid salt and piperazine-dodecanedioic acid salt containing nylon 1 chain segments, which are prepared by salifying in the step 3, are respectively:
10. a method of preparation according to claim 3, characterized in that: in the step 4, the piperazine-polyamide salt containing the nylon 1 chain segment and the piperazine-dodecanedioic acid salt obtained in the step 3 are added into a polymerization reaction kettle together for copolymerization reaction, water, a catalyst, an antioxidant and the like are also added, the mass of the added water is 1/2 of the total mass of the nylon salt, and the mass of the added catalyst and the mass of the added antioxidant are respectively 0.3-0.5 wt% of the total mass of the nylon salt.
11. A method of preparation according to claim 3, characterized in that: in the step 4, the reaction temperature of the prepolymerization reaction is 160-190 ℃, the reaction time is 2 hours, and the reaction pressure is controlled below the saturated vapor pressure of water, specifically 0.3-0.5MPa; the tackifying reaction temperature is 230-250 ℃, and the reaction is carried out for 2 hours at constant pressure; and then a circulating water type vacuum pump is adopted for vacuumizing, the vacuum degree is 0.09MPa, and the reaction time is 2 hours.
12. A method of preparation according to claim 3, characterized in that: in the step 5, the hot press molding process of the film is that plasticizing is firstly carried out for 10 minutes at 210-230 ℃; hot-pressing at 210-230 deg.c for 5 min at 10MPa; finally cold pressing for 3 minutes at room temperature, wherein the pressure is 10MPa.
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