CN117888386A - Preparation method of poly (p-phenylene terephthamide) PPTA fiber paper containing soft chain segment - Google Patents
Preparation method of poly (p-phenylene terephthamide) PPTA fiber paper containing soft chain segment Download PDFInfo
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- CN117888386A CN117888386A CN202311797936.7A CN202311797936A CN117888386A CN 117888386 A CN117888386 A CN 117888386A CN 202311797936 A CN202311797936 A CN 202311797936A CN 117888386 A CN117888386 A CN 117888386A
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- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 title claims abstract description 210
- 239000000835 fiber Substances 0.000 title claims abstract description 118
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000007731 hot pressing Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 88
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 30
- 239000006184 cosolvent Substances 0.000 claims description 19
- 150000001263 acyl chlorides Chemical group 0.000 claims description 14
- 238000007865 diluting Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 5
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims description 3
- 239000012454 non-polar solvent Substances 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 claims 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229920006253 high performance fiber Polymers 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 38
- 239000000178 monomer Substances 0.000 description 36
- 238000012360 testing method Methods 0.000 description 28
- 230000009471 action Effects 0.000 description 26
- 238000003756 stirring Methods 0.000 description 23
- 238000010008 shearing Methods 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 230000009477 glass transition Effects 0.000 description 12
- 239000012046 mixed solvent Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000005057 refrigeration Methods 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 230000000087 stabilizing effect Effects 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 229920003235 aromatic polyamide Polymers 0.000 description 6
- 230000003993 interaction Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 101150043088 DMA1 gene Proteins 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention relates to a preparation method of poly (p-phenylene terephthamide) PPTA fiber paper containing a flexible chain segment, which comprises the following steps: and uniformly mixing the PPTA finished product chopped fiber with the PPTA fibrid containing the soft chain segment, and carrying out hot pressing and drying to obtain the PPTA high-performance fiber paper containing the soft chain segment. The PPTA fiber paper prepared by the method has excellent performance, simple preparation process and lower equipment requirement, and is beneficial to industrial production.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of PPTA fiber paper containing flexible chain segments.
Background
The PPTA product generally has excellent thermal performance, mechanical performance, electrochemical stability and the like, is widely applied to the fields of national defense, military industry, aerospace and the like, and is also an ideal material for preparing high-performance fiber paper due to the characteristics of large molecular chain bond energy, high rigidity, strong molecular chain interaction and the like of the PPTA. However, since PPTA is poorly soluble in conventional organic solvents and its melting point is higher than its decomposition temperature, it is difficult to achieve effective interfacial bonding of PPTA fibrids and chopped fibers in a micro-molten state by conventional hot pressing processes, affecting the overall mechanical properties of the fibrous paper. Therefore, it is important to improve the interfacial bonding force between two phases inside the fiber paper.
Chinese patent No. CN 101687382a discloses a honeycomb of poly (p-phenylene terephthalamide) paper containing an aliphatic polyamide binder and articles made from the honeycomb. The method is that aliphatic polyamide adhesives such as nylon 610, nylon 6, nylon 66 and the like with different proportions are used as void filling thermosetting resin, and are blended with PPTA fibers, and the PPTA fiber paper with excellent mechanical properties is prepared through hot pressing. However, the content of the aliphatic structure doped in the PPTA fiber paper prepared by the method is higher, and the overall thermal property, the electrical insulation property and the chemical stability of the paper are inevitably influenced.
The Chinese patent No. 114481677A discloses a modified para-aramid paper (PPTA paper) and a preparation method and application thereof, wherein in the method, p-phenylenediamine, terephthaloyl chloride and a fluorescent unit with aggregation-induced emission characteristic are taken as raw materials to carry out polymerization reaction to obtain a polymerization product, and the polymerization product is stirred, crushed and dried to obtain modified para-aramid crude fiber; the modified para-aramid fiber dispersion liquid is obtained through alkali treatment, and the para-aramid paper with excellent tensile strength and fluorescence performance is obtained after vacuum suction filtration and hot pressing. However, the para-aramid paper prepared by the method has weak internal interaction, low rigidity and poor tearing strength, and is difficult to meet the requirements of the market on high-performance PPTA fiber paper.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of PPTA fiber paper containing flexible chain segments, and overcomes the defects of complex production process, higher cost, poorer tearing strength and the like of the existing para-aramid fiber paper.
The invention discloses a PPTA fiber paper containing a flexible chain segment, which comprises PPTA fibers containing a flexible chain segment and PPTA chopped fibers.
Preferably, the flexible segment-containing PPTA fiber is a fibrid containing a flexible segment PPTA, wherein the structure of the flexible segment-containing PPTA includes:
one or more of the following; wherein m=10-40; n=1-40.
Preferably, the mass ratio of the PPTA chopped fibers to the PPTA fibrids containing the soft chain segments is 2:8-6:4; the diameter of the PPTA chopped fiber is 10-30 mu m, and the length is 4-8 mm.
The invention discloses a preparation method of poly (p-phenylene terephthamide) PPTA fiber paper containing a flexible chain segment, which comprises the following steps:
(1) In a dry inert gas system, carrying out low-temperature solution polycondensation by controlling the mole ratio of p-phenylenediamine PPDA and terephthaloyl chloride TPC to prepare a PPTA solution with low polymerization degree, and then carrying out secondary copolymerization on the PPTA solution and a prepolymer with a certain polymerization degree and a soft segment to obtain the PPTA solution with the soft segment;
(2) Diluting the PPTA solution containing the soft chain segment to the solid content of 2-6wt%, and then injecting into a high-speed shearing coagulation bath for coagulation forming to obtain PPTA fibrids containing the soft chain segment;
(3) And mixing the PPTA fibrids containing the soft chain segments and the PPTA chopped fibers, and carrying out hot pressing and drying to obtain the PPTA fiber paper containing the soft chain segments.
Preferably, the mole ratio of the p-phenylenediamine PPDA to the terephthaloyl chloride TPC in the step (1) is 0.9-1.1; the PPTA solution is prepared by polycondensation, wherein the polymerization degree of the PPTA is 10-40.
Preferably, the solvent adopted in the step (1) is a polar solvent system, wherein the polar solvent system comprises a solvent and a cosolvent, and the solvent is one or more of N-methylpyrrolidone, N-ethylpyrrolidone, N-dimethylacetamide and benzimidazole ionic liquid; the cosolvent is one or more of alkali metal or alkaline earth metal chlorides, and the content of the cosolvent in the solvent system is 5-20% (wt).
The cosolvent comprises at least one of lithium chloride and calcium chloride.
Preferably, the prepolymer containing the soft chain segment in the step (1) is one or more of ether bond, sulfide bond, sulfone bond, aliphatic, diacetylene, cycloaliphatic substituted p-benzene and m-benzene structures; the polymerization degree of the prepolymer containing the soft chain segment is 1-40, and the end group is blocked by acyl chloride group or amino group.
Further preferably, the structure of the prepolymer containing a soft segment is one or more of the following (numbered A-I):
A:
B:
C:
D:
E:
F:
G:
H:
where n=1-40.
Preferably, the mole ratio of the secondary copolymerized PPTA to the prepolymer containing the soft segment in the step (1) is 0.1-10.
Preferably, the temperature of the low-temperature solution polycondensation in the step (1) is-15 ℃ and the time is 10-60 min; the temperature of the secondary copolymerization is 5-20 ℃ and the time is 30-90 min.
Preferably, the solidifying bath in the step (2) is a non-solvent mixed solution with the concentration of 0 to 80 weight percent; wherein the non-solvent is one or more of non-polar solvents; the solvent is one or more of N-methyl pyrrolidone, N-ethyl pyrrolidone, N-dimethylacetamide and benzimidazole ionic liquid.
Further, the non-solvent is one or more of water, ethanol and other non-polar solvents.
And (2) injecting the PPTA diluted solution containing the soft chain segment into a solvent/non-solvent mixed system with high-speed shearing, stirring, crushing and dispersing the PPTA solution drops containing the soft chain segment, stretching under the shearing action to deform, and simultaneously starting solidification and forming under the non-solvent action to obtain the PPTA fibrids containing the soft chain segment.
Preferably, the flexible segment-containing PPTA fibrids in the step (2) have a diameter of 50-800 μm.
Preferably, the mass ratio of the PPTA chopped fibers to the PPTA fibrids containing the soft chain segments in the step (3) is 2:8-6:4; the diameter of the PPTA chopped fiber is 10-30 mu m, and the length is 4-8 mm.
Preferably, the hot pressing temperature in the step (3) is 200-350 ℃, the hot pressing pressure is 5-15 MPa, and the hot pressing time is 10-50 min.
The invention provides the PPTA fiber paper containing the flexible chain segment poly (p-phenylene terephthamide) prepared by the method.
The flexible chain segment-containing poly (p-phenylene terephthamide) PPTA fiber paper is applied to the fields of insulating materials and honeycomb core materials, such as high-temperature resistant heat insulating materials, high-performance paper-based composite materials such as honeycomb core materials and the like.
The PPTA fiber paper containing the soft chain segment has higher internal two-phase interface shear strength, strong overall rigidity of the fiber paper and excellent tearing strength.
The invention selects a prepolymer with a flexible structure to prepare PPTA fibrid containing a flexible chain segment, takes the PPTA fibrid containing the flexible chain segment which can show micro-melting phenomenon in the hot pressing process as a filler and a binder, and prepares the PPTA fiber paper through hot pressing and drying.
Advantageous effects
(1) The invention adopts the monomer with the flexible structure to prepare the PPTA fibrid containing the flexible chain segment, the reaction activity of the monomer is relatively weakened, the preparation stability is high, the polymerization reaction process of the PPTA solution containing the flexible chain segment is easier to control, and the invention is beneficial to the subsequent processing application;
(2) According to the invention, the PPTA chopped fibers and the PPTA fibrids containing the soft chain segments are uniformly dispersed in water, and the PPTA fiber paper containing the soft chain segments is obtained through hot pressing and drying, so that the processing property is higher, the process is simple, and the industrial production is facilitated;
(3) According to the invention, the flexible chain segment PPTA fibrid containing micro-melting phenomenon can be selected as the filler and the binder in the hot pressing process, the existence of the flexible chain segment can effectively destroy the integral arrangement regularity of the molecular chain and weaken the interaction between the molecular chains, the micro-melting phenomenon is generated on the surface of the flexible chain segment PPTA fibrid containing the flexible chain segment in the hot pressing process, the interface interaction of each part in the paper is improved, and the integral mechanical property of the flexible chain segment PPTA fiber paper is improved.
Drawings
Fig. 1 is a scanning electron microscope image of an embodiment.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
PPTA chopped fiber, 10 μm in diameter and 6mm,8mm,9mm in length, respectively, was purchased from Nicotiana tabacum and New Material Co., ltd.
The adopted prepolymer containing the soft chain segment with the number of B has the structural formula:
the adopted prepolymer containing the soft chain segment and with the number of E has the structural formula:
in the invention, the performance of the PPTA paper is measured by the following method:
(1) Observation of sample morphology
Scanning the fibrid and the morphology of the paper-based material prepared by the fibrid by adopting a SU8010 type cold field emission Scanning Electron Microscope (SEM), and setting the accelerating voltage to be 10kV.
(2) Mechanical property test
Carrying out mechanical property test on PPTA paper by adopting a Metrele C44-104 universal electronic tester, wherein the width of a sample is 10mm, the clamping distance is 20mm, the test temperature is room temperature, and the stretching speed is 5mm/min, so as to carry out paper tensile strength test; the tear resistance of PPTA paper was tested using an IMT-224 model tear strength tester according to astm d624-2012 standard.
(3) Dynamic thermo-mechanical Performance (DMA) testing
The thermal mechanical properties of the prepared PPTA paper are measured by a DMA1 type Metreler dynamic thermal mechanical analyzer, the sample size is a spline of 10mm multiplied by 5mm, the heating rate is 5 ℃/min, the heating interval is 30-400 ℃, the frequency is 1Hz, and the test is carried out in a stretching mode.
Example 1
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution, adding 0.04mol of PPDA monomer, stirring at room temperature until the PPDA monomer is completely dissolved, transferring the reaction device into a refrigeration circulation bath, cooling to-10 ℃, after the temperature of the reaction system is stable, adding 0.044mol of TPC monomer, rapidly stirring and reacting, wherein the viscosity of the system is rapidly increased, and after reacting for 10min, the system is basically stable, so as to obtain a uniform and stable PPTA polymer system with the polymerization degree of 19 capped by acyl chloride groups; adding 0.01mol of prepolymer containing soft chain segment with polymerization degree of 20 and number of B, continuously reacting at 5 ℃ for 30min to obtain PPTA solution containing soft chain segment, and diluting the PPTA solution to a solution with solid content of 2wt% for later use.
(2) Injecting the PPTA diluted solution containing the soft segment obtained in the step (1) into 80% NMP-H sheared at high speed 2 In the O mixed solvent, the PPTA solution drops containing the soft chain segments are stirred, smashed and dispersed, and simultaneously are stretched and deformed under the shearing action, and simultaneously are in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids containing the soft chain segments.
(3) Mixing PPTA chopped fibers with the diameter of 10 mu m and the length of 6mm into the PPTA fibrids containing the soft chain segments, which are obtained in the step (2), controlling the mass ratio of the chopped fibers to the fibrids to be 2:8, hot-pressing the chopped fibers for 10min at 280 ℃ under the environment of 10MPa, and drying the chopped fibers to obtain the PPTA fiber paper containing the soft chain segments.
As shown in FIG. 1 (b), the SEM image of the PPTA fiber paper obtained by the test shows that the glass transition temperature of the paper obtained by the DMA test is 295 ℃ and the paper tearing index is 32 mN.m 2 ·g -1 The tensile strength was 54.3MPa.
Example 2
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution, adding 0.036mol of PPDA monomer, stirring at room temperature until the PPDA monomer is completely dissolved, transferring the reaction device into a refrigeration circulation bath, cooling to-10 ℃, after the temperature of the reaction system is stable, adding 0.044mol of TPC monomer, rapidly stirring and reacting, at this moment, rapidly increasing the viscosity of the system, and after 10min of reaction, basically stabilizing to obtain a uniform and stable PPTA polymer system with the polymerization degree of 21 capped by acyl chloride groups; adding 0.01mol of prepolymer containing soft chain segment with polymerization degree of 20 and number of B, continuously reacting at 5 ℃ for 30min to obtain PPTA solution containing soft chain segment, and diluting the PPTA solution to a solution with solid content of 2wt% for later use.
(2) Injecting the PPTA diluted solution containing the soft segment obtained in the step (1) into 80% NMP-H sheared at high speed 2 In the O mixed solvent, the PPTA solution drops containing the soft chain segments are stirred, smashed and dispersed, and simultaneously are stretched and deformed under the shearing action, and simultaneously are in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids containing the soft chain segments.
(3) Mixing PPTA chopped fibers with the diameter of 10 mu m and the length of 6mm into the PPTA fibrids containing the soft chain segments, which are obtained in the step (2), controlling the mass ratio of the chopped fibers to the fibrids to be 2:8, hot-pressing the chopped fibers for 10min at 280 ℃ under the environment of 10MPa, and drying the chopped fibers to obtain the PPTA fiber paper containing the soft chain segments.
As shown in FIG. 1 (c), the SEM image of the PPTA fiber paper obtained by the test shows that the glass transition temperature of the paper obtained by the DMA test is 294 ℃ and the paper tearing index is 33 mN.m 2 ·g -1 The tensile strength was 56.2MPa.
Example 3
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution and 0.036mol of PPDA monomer were added, stirred at room temperature until dissolution was complete, howeverTransferring the reaction device into a refrigeration circulation bath to be cooled to minus 10 ℃, after the temperature of a reaction system is stable, adding 0.044mol of TPC monomer, and rapidly stirring and reacting, wherein the viscosity of the system is rapidly increased, and basically stabilizing the reaction after 10 minutes, so as to obtain a uniform and stable PPTA polymer system with the polymerization degree of 21 and end capped by acyl chloride groups; adding 0.01mol of prepolymer containing soft chain segment with the polymerization degree of 20 and the number of E for continuous reaction, wherein the reaction temperature is 5 ℃, and the reaction time is 30min to obtain the PPTA solution containing the soft chain segment, and diluting the PPTA solution into the solution with the solid content of 2wt% for standby.
(2) Injecting the PPTA diluted solution containing the soft segment obtained in the step (1) into 80% NMP-H sheared at high speed 2 In the O mixed solvent, the PPTA solution drops containing the soft chain segments are stirred, smashed and dispersed, and simultaneously are stretched and deformed under the shearing action, and simultaneously are in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids containing the soft chain segments.
(3) Mixing PPTA chopped fibers with the diameter of 10 mu m and the length of 6mm into the PPTA fibrids containing the soft chain segments, which are obtained in the step (2), controlling the mass ratio of the chopped fibers to the fibrids to be 2:8, hot-pressing the chopped fibers for 10min at 280 ℃ under the environment of 10MPa, and drying the chopped fibers to obtain the PPTA fiber paper containing the soft chain segments.
As shown in FIG. 1 (d), the SEM image of the PPTA fiber paper obtained by the test shows that the glass transition temperature of the paper obtained by the DMA test is 290 ℃ and the paper tearing index is 35 mN.m 2 ·g -1 The tensile strength was 57.4MPa.
Example 4
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution, adding 0.036mol of PPDA monomer, stirring at room temperature until the PPDA monomer is completely dissolved, transferring the reaction device into a refrigeration circulation bath, cooling to-10 ℃, after the temperature of the reaction system is stable, adding 0.044mol of TPC monomer, rapidly stirring and reacting, at this moment, rapidly increasing the viscosity of the system, and after 10min of reaction, basically stabilizing to obtain a uniform and stable PPTA polymer system with the polymerization degree of 21 capped by acyl chloride groups; 0.01mol of soft segment-containing segment having a degree of polymerization 40 of the number E is addedThe prepolymer is continuously reacted at the temperature of 5 ℃ for 30min to obtain a solution containing the flexible chain segment PPTA, and the solution is diluted to a solution with the solid content of 2wt% for standby.
(2) Injecting the PPTA diluted solution containing the soft segment obtained in the step (1) into 80% NMP-H sheared at high speed 2 In the O mixed solvent, the PPTA solution drops containing the soft chain segments are stirred, smashed and dispersed, and simultaneously are stretched and deformed under the shearing action, and simultaneously are in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids containing the soft chain segments.
(3) Mixing PPTA chopped fibers with the diameter of 10 mu m and the length of 6mm into the PPTA fibrids containing the soft chain segments, which are obtained in the step (2), controlling the mass ratio of the chopped fibers to the fibrids to be 2:8, hot-pressing the chopped fibers for 10min at 280 ℃ under the environment of 10MPa, and drying the chopped fibers to obtain the PPTA fiber paper containing the soft chain segments.
As shown in FIG. 1 (e), the SEM image of the PPTA fiber paper obtained by the test shows that the glass transition temperature of the paper obtained by the DMA test is 295 ℃, and the paper tearing index is 35.9 mN.m 2 ·g -1 The tensile strength was 59.1MPa.
Example 5
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution, adding 0.036mol of PPDA monomer, stirring at room temperature until the PPDA monomer is completely dissolved, transferring the reaction device into a refrigeration circulation bath, cooling to-10 ℃, after the temperature of the reaction system is stable, adding 0.044mol of TPC monomer, rapidly stirring and reacting, at this moment, rapidly increasing the viscosity of the system, and after 10min of reaction, basically stabilizing to obtain a uniform and stable PPTA polymer system with the polymerization degree of 21 capped by acyl chloride groups; adding 0.216mol of prepolymer containing soft chain segment with the polymerization degree of 40 of E, continuously reacting at the temperature of 5 ℃ for 30min to obtain PPTA solution containing soft chain segment, and diluting the PPTA solution to a solution with the solid content of 2wt% for later use.
(2) Injecting the PPTA diluted solution containing the soft segment obtained in the step (1) into 80% NMP-H sheared at high speed 2 In the O mixed solvent, PPTA solution drops containing flexible chain segmentsIs stirred, broken and dispersed, and simultaneously is stretched and deformed under the shearing action, and simultaneously is in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids containing the soft chain segments.
(3) Mixing PPTA chopped fibers with the diameter of 10 mu m and the length of 6mm into the PPTA fibrids containing the soft chain segments, which are obtained in the step (2), controlling the mass ratio of the chopped fibers to the fibrids to be 2:8, hot-pressing the chopped fibers for 10min at 280 ℃ under the environment of 10MPa, and drying the chopped fibers to obtain the PPTA fiber paper containing the soft chain segments.
As shown in FIG. 1 (g), the SEM image of the PPTA fiber paper obtained by the test shows that the glass transition temperature of the paper obtained by the DMA test is 289 ℃, and the paper tearing index is 36.3 mN.m 2 ·g -1 The tensile strength was 62.3MPa.
Example 6
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution, adding 0.036mol of PPDA monomer, stirring at room temperature until the PPDA monomer is completely dissolved, transferring the reaction device into a refrigeration circulation bath, cooling to-10 ℃, after the temperature of the reaction system is stable, adding 0.044mol of TPC monomer, rapidly stirring and reacting, at this moment, rapidly increasing the viscosity of the system, and after 10min of reaction, basically stabilizing to obtain a uniform and stable PPTA polymer system with the polymerization degree of 21 capped by acyl chloride groups; adding 0.216mol of prepolymer containing soft chain segment with the polymerization degree of 40 of E, continuously reacting at the temperature of 5 ℃ for 30min to obtain a solution containing soft chain segment PPTA, and diluting the solution into a solution with the solid content of 4wt% for later use.
(2) Injecting the PPTA diluted solution containing the soft segment obtained in the step (1) into 80% NMP-H sheared at high speed 2 In the O mixed solvent, the PPTA solution drops containing the soft chain segments are stirred, smashed and dispersed, and simultaneously are stretched and deformed under the shearing action, and simultaneously are in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids containing the soft chain segments.
(3) Mixing PPTA chopped fibers with the diameter of 10 mu m and the length of 6mm into the PPTA fibrids containing the soft chain segments, which are obtained in the step (2), controlling the mass ratio of the chopped fibers to the fibrids to be 2:8, hot-pressing the chopped fibers for 10min at 280 ℃ under the environment of 10MPa, and drying the chopped fibers to obtain the PPTA fiber paper containing the soft chain segments.
As shown in FIG. 1 (f), the SEM image of the PPTA fiber paper obtained by the test shows that the glass transition temperature of the paper obtained by the DMA test is 289 ℃, and the paper tearing index is 36 mN.m 2 ·g -1 The tensile strength was 60MPa.
Example 7
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution, adding 0.036mol of PPDA monomer, stirring at room temperature until the PPDA monomer is completely dissolved, transferring the reaction device into a refrigeration circulation bath, cooling to-10 ℃, after the temperature of the reaction system is stable, adding 0.044mol of TPC monomer, rapidly stirring and reacting, at this moment, rapidly increasing the viscosity of the system, and after 10min of reaction, basically stabilizing to obtain a uniform and stable PPTA polymer system with the polymerization degree of 21 capped by acyl chloride groups; adding 0.216mol of prepolymer containing soft chain segment with the polymerization degree of 40 of E, continuously reacting at the temperature of 5 ℃ for 30min to obtain PPTA solution containing soft chain segment, and diluting the PPTA solution to a solution with the solid content of 2wt% for later use.
(2) Injecting the PPTA diluted solution containing the soft segment obtained in the step (1) into 80% NMP-H sheared at high speed 2 In the O mixed solvent, the PPTA solution drops containing the soft chain segments are stirred, smashed and dispersed, and simultaneously are stretched and deformed under the shearing action, and simultaneously are in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids containing the soft chain segments.
(3) Mixing PPTA chopped fibers with the diameter of 10 mu m and the length of 6mm into the PPTA fibrids containing the soft chain segments, which are obtained in the step (2), controlling the mass ratio of the chopped fibers to the fibrids to be 3:7, hot-pressing the chopped fibers for 10min at 280 ℃ under the environment of 10MPa, and drying the chopped fibers to obtain the PPTA fiber paper containing the soft chain segments.
As shown in FIG. 1 (h), the SEM image of the PPTA fiber paper obtained by the test shows that the glass transition temperature of the paper obtained by the DMA test is 285 ℃ and the paper tearing index is 36.5 mN.m 2 ·g -1 The tensile strength was 64MPa.
Example 8
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution, adding 0.036mol of PPDA monomer, stirring at room temperature until the PPDA monomer is completely dissolved, transferring the reaction device into a refrigeration circulation bath, cooling to-10 ℃, after the temperature of the reaction system is stable, adding 0.044mol of TPC monomer, rapidly stirring and reacting, at this moment, rapidly increasing the viscosity of the system, and after 10min of reaction, basically stabilizing to obtain a uniform and stable PPTA polymer system with the polymerization degree of 21 capped by acyl chloride groups; adding 0.216mol of prepolymer containing soft chain segment with the polymerization degree of 40 of E, continuously reacting at the temperature of 5 ℃ for 30min to obtain PPTA solution containing soft chain segment, and diluting the PPTA solution to a solution with the solid content of 2wt% for later use.
(2) Injecting the PPTA diluted solution containing the soft segment obtained in the step (1) into 80% NMP-H sheared at high speed 2 In the O mixed solvent, the PPTA solution drops containing the soft chain segments are stirred, smashed and dispersed, and simultaneously are stretched and deformed under the shearing action, and simultaneously are in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids containing the soft chain segments.
(3) Mixing PPTA chopped fibers with the diameter of 10 mu m and the length of 6mm into the PPTA fibrids containing the soft chain segments, which are obtained in the step (2), controlling the mass ratio of the chopped fibers to the fibrids to be 3:7, hot-pressing the chopped fibers for 10min at 310 ℃ under the environment of 10MPa, and drying the chopped fibers to obtain the PPTA fiber paper containing the soft chain segments.
As shown in FIG. 1 (i), the SEM image of the PPTA fiber paper obtained by the test shows that the glass transition temperature of the paper obtained by the DMA test is 285 ℃ and the paper tearing index is 38 mN.m 2 ·g -1 The tensile strength was 67MPa.
Example 9
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution, and 0.036mol of PPDA monomer was added, stirred at room temperature until dissolution was complete,transferring the reaction device into a refrigeration circulation bath to be cooled to minus 10 ℃, after the temperature of a reaction system is stable, adding 0.044mol of TPC monomer, and rapidly stirring and reacting, wherein the viscosity of the system is rapidly increased, and basically stabilizing the reaction after 10 minutes, so as to obtain a uniform and stable PPTA polymer system with the polymerization degree of 21 and end capped by acyl chloride groups; adding 0.216mol of prepolymer containing soft chain segment with the polymerization degree of 40 of E, continuously reacting at the temperature of 5 ℃ for 30min to obtain PPTA solution containing soft chain segment, and diluting the PPTA solution to a solution with the solid content of 2wt% for later use.
(2) Injecting the PPTA diluted solution containing the soft segment obtained in the step (1) into 80% NMP-H sheared at high speed 2 In the O mixed solvent, the PPTA solution drops containing the soft chain segments are stirred, smashed and dispersed, and simultaneously are stretched and deformed under the shearing action, and simultaneously are in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids containing the soft chain segments.
(3) Mixing PPTA chopped fiber with the diameter of 10 mu m and the length of 8mm into the PPTA fibrid containing the soft chain segment, which is obtained in the step (2), controlling the mass ratio of the chopped fiber to the fibrid to be 3:7, hot-pressing the chopped fiber for 10min at 310 ℃ under the environment of 10MPa, and drying to obtain the PPTA fiber paper containing the soft chain segment.
As shown in FIG. 1 (j), the SEM image of the PPTA fiber paper obtained by the test shows that the glass transition temperature of the paper obtained by the DMA test is 285 ℃ and the paper tearing index is 36.4 mN.m 2 ·g -1 The tensile strength was 59.8MPa.
Comparative example 1
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution, adding 0.036mol of PPDA monomer, stirring at room temperature until the PPDA monomer is completely dissolved, transferring the reaction device into a refrigeration circulation bath, cooling to-10 ℃, after the temperature of the reaction system is stable, adding 0.044mol of TPC monomer, rapidly stirring and reacting, at this moment, rapidly increasing the viscosity of the system, and after 10min of reaction, basically stabilizing to obtain a uniform and stable PPTA polymer system with the polymerization degree of 21 capped by acyl chloride groups; flexible, flexible-containing polymers having a degree of polymerization 40 of 0.216mol of the number E were addedThe chain segment prepolymer continues to react, the reaction temperature is 5 ℃, the reaction time is 30min, the solution containing the flexible chain segment PPTA is obtained, and the solution is diluted into a solution with the solid content of 2wt% for standby.
(2) Injecting the PPTA diluted solution containing the soft segment obtained in the step (1) into 80% NMP-H sheared at high speed 2 In the O mixed solvent, the PPTA solution drops containing the soft chain segments are stirred, smashed and dispersed, and simultaneously are stretched and deformed under the shearing action, and simultaneously are in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids containing the soft chain segments.
(3) Mixing the PPTA chopped fiber with the diameter of 10 mu m and the length of 9mm into the PPTA fibrid containing the soft chain segment, which is obtained in the step (2), controlling the mass ratio of the chopped fiber to the fibrid to be 3:7, hot-pressing the chopped fiber for 10min at 310 ℃ under the environment of 10MPa, and drying to obtain the PPTA fiber paper containing the soft chain segment.
As shown in FIG. 1 (k), the SEM image of the PPTA fiber paper obtained by the test shows that the glass transition temperature of the paper obtained by the DMA test is 285 ℃ and the paper tearing index is 31.4 mN.m 2 ·g -1 The tensile strength was 54.1MPa.
Comparative example 2
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution, adding 0.036mol of PPDA monomer, stirring at room temperature until the PPDA monomer is completely dissolved, transferring the reaction device into a refrigeration circulation bath, cooling to-10 ℃, after the temperature of the reaction system is stable, adding 0.044mol of TPC monomer, rapidly stirring and reacting, at this moment, rapidly increasing the viscosity of the system, and after 10min of reaction, basically stabilizing to obtain a uniform and stable PPTA polymer system with the polymerization degree of 21 capped by acyl chloride groups; adding 0.216mol of prepolymer containing soft chain segment with the polymerization degree of 40 of E, continuously reacting at the temperature of 5 ℃ for 30min to obtain PPTA solution containing soft chain segment, and diluting the PPTA solution to a solution with the solid content of 2wt% for later use.
(2) Injecting the PPTA diluted solution containing the soft segment obtained in the step (1) into 80% NMP-H sheared at high speed 2 In the O mixed solvent, the solution containing the flexible chain segment PPTAThe liquid drops are stirred, broken and dispersed, and are stretched and deformed under the shearing action, and at the same time, the liquid drops are dissolved in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids containing the soft chain segments.
(3) Mixing PPTA chopped fiber with the diameter of 10 mu m and the length of 8mm into the PPTA fibrid containing the soft chain segment, which is obtained in the step (2), controlling the mass ratio of the chopped fiber to the fibrid to be 7:3, hot-pressing the chopped fiber for 10min at 310 ℃ under the environment of 10MPa, and drying to obtain the PPTA fiber paper containing the soft chain segment.
As shown in FIG. 1 (l), the SEM image of the PPTA fiber paper obtained by the test shows that the glass transition temperature of the paper obtained by the DMA test is 293 ℃, and the paper tearing index is 30.4 mN.m 2 ·g -1 The tensile strength was 49MPa.
Comparative example 3
(1) In a dry system with a humidity lower than 50% under nitrogen atmosphere, 100mL of NMP-CaCl was added to a three-necked flask 2 (cosolvent content 5 wt%) solution, adding 0.036mol of PPDA monomer, stirring at room temperature until the PPDA monomer is completely dissolved, transferring the reaction device into a refrigeration circulation bath, cooling to-10 ℃, after the reaction system temperature is stable, adding 0.044mol of TPC monomer, rapidly stirring and reacting, at this time, rapidly raising the viscosity of the system, after reacting for 10min, basically stabilizing, obtaining a uniform and stable PPTA polymer system with the end-capped acyl chloride group and the polymerization degree of 21, and diluting the PPTA polymer system into a solution with the solid content of 2wt% for standby.
(2) Injecting the PPTA diluted solution without the soft segment obtained in the step (1) into 80% NMP-H with high-speed shearing 2 In the O mixed solvent, PPTA solution drops are stirred, smashed and dispersed, and simultaneously are stretched and deformed under the shearing action, and simultaneously are in a non-solvent H 2 And (3) starting to solidify and form under the action of O to obtain the PPTA fibrids.
(3) Mixing the PPTA chopped fiber with the diameter of 10 mu m and the length of 8mm into the PPTA fibrid obtained in the step (2), controlling the mass ratio of the chopped fiber to the fibrid to be 3:7, hot-pressing the PPTA chopped fiber for 10min at 310 ℃ under the environment of 10MPa, and drying to obtain the PPTA fiber paper containing the soft chain segment.
Tested by testingAs shown in FIG. 1 (a), the SEM image of the obtained PPTA fiber paper shows that the paper has no glass transition temperature and the paper tear index is 15 mN.m 2 ·g -1 The tensile strength was 29MPa.
Claims (10)
1. A flexible chain segment-containing poly (p-phenylene terephthalamide) PPTA fiber paper, which is characterized in that the fiber paper component comprises flexible chain segment-containing PPTA fibers and PPTA chopped fibers.
2. The fiber paper according to claim 1, wherein the flexible segment-containing PPTA fibers are fibrids of flexible segment-containing PPTA, wherein the structure of the flexible segment-containing PPTA comprises:
one or more of the following; wherein m=10-40; n=1-40;
the mass ratio of the PPTA chopped fibers to the PPTA fibrids containing the soft chain segments is 2:8-6:4; the diameter of the PPTA chopped fiber is 10-30 mu m, and the length is 4-8 mm.
3. A method for preparing poly (p-phenylene terephthamide) PPTA fiber paper containing a flexible chain segment, which comprises the following steps:
(1) In a dry inert gas system, carrying out low-temperature solution polycondensation on p-phenylenediamine PPDA and terephthaloyl chloride TPC to obtain a PPTA solution, and then carrying out secondary copolymerization on the PPTA solution and a prepolymer containing a soft chain segment to obtain the PPTA solution containing the soft chain segment;
(2) Diluting the PPTA solution containing the soft chain segment, and then injecting the diluted PPTA solution into a sheared coagulating bath for coagulating and forming to obtain PPTA fibrids containing the soft chain segment;
(3) And mixing the PPTA fibrids containing the soft chain segments and the PPTA chopped fibers, and carrying out hot pressing and drying to obtain the PPTA fiber paper containing the soft chain segments.
4. The method according to claim 3, wherein the molar ratio of p-phenylenediamine PPDA to terephthaloyl chloride TPC in step (1) is 0.9 to 1.1; the PPTA solution is prepared by polycondensation, wherein the polymerization degree of the PPTA is 10-40; the solvent adopted in the step (1) is a polar solvent system, wherein the polar solvent system comprises a solvent and a cosolvent; wherein the solvent is one or more of N-methyl pyrrolidone, N-ethyl pyrrolidone, N-dimethylacetamide and benzimidazole ionic liquid; the cosolvent is one or more of alkali metal or alkaline earth metal chlorides, and the content of the cosolvent in the solvent system is 5-20% (wt).
5. The method according to claim 3, wherein the prepolymer containing the soft segment in the step (1) is one or more of ether bond, sulfide bond, sulfone bond, aliphatic, diacetylene, cycloaliphatic, substituted p-benzene and m-benzene structure; the polymerization degree of the prepolymer containing the soft chain segment is 1-40, and the end group is blocked by acyl chloride group or amino group;
the molar ratio of the secondary copolymerized PPTA to the prepolymer containing the soft chain segment in the step (1) is 0.1-10.
6. The method according to claim 5, wherein the prepolymer containing a soft segment is:
one or more of the following; wherein n=1-40。
7. The process according to claim 3, wherein the low temperature solution polycondensation in step (1) is carried out at a temperature of-15℃to 15℃for a period of 10min to 60min; the temperature of the secondary copolymerization is 5-20 ℃ and the time is 30-90 min.
8. The method according to claim 3, wherein the coagulation bath in the step (2) is a non-solvent mixed solution of 0wt% to 80 wt%; wherein the non-solvent is one or more of non-polar solvents; wherein the solvent is one or more of N-methyl pyrrolidone, N-ethyl pyrrolidone, N-dimethylacetamide and benzimidazole ionic liquid.
The diameter of the PPTA fibrid containing the flexible chain segment in the step (2) is 50-800 mu m.
9. The method according to claim 3, wherein the mass ratio of the PPTA chopped fibers to the PPTA fibrids containing the soft chain segments in the step (3) is 2:8-6:4; the diameter of the PPTA chopped fiber is 10-30 mu m, and the length is 4-8 mm;
the hot pressing temperature in the step (3) is 200-350 ℃, the hot pressing pressure is 5-15 MPa, and the hot pressing time is 10-50 min.
10. Use of the poly (p-phenylene terephthamide) PPTA fiber paper containing the soft segment according to claim 1 in the fields of insulating materials and honeycomb cores.
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