CN115819764B - Polyimide fiber and preparation method thereof - Google Patents
Polyimide fiber and preparation method thereof Download PDFInfo
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- CN115819764B CN115819764B CN202211500605.8A CN202211500605A CN115819764B CN 115819764 B CN115819764 B CN 115819764B CN 202211500605 A CN202211500605 A CN 202211500605A CN 115819764 B CN115819764 B CN 115819764B
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- 239000000835 fiber Substances 0.000 title claims abstract description 81
- 239000004642 Polyimide Substances 0.000 title claims abstract description 43
- 229920001721 polyimide Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 21
- 238000009987 spinning Methods 0.000 claims abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 11
- PAPDRIKTCIYHFI-UHFFFAOYSA-N 4-[3,5-bis(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC(OC=2C=CC(N)=CC=2)=CC(OC=2C=CC(N)=CC=2)=C1 PAPDRIKTCIYHFI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002166 wet spinning Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000004952 Polyamide Substances 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract description 3
- 229920002647 polyamide Polymers 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 26
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 20
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 14
- 150000004985 diamines Chemical class 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000001112 coagulating effect Effects 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 238000009998 heat setting Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000007906 compression Methods 0.000 abstract description 15
- 230000006835 compression Effects 0.000 abstract description 14
- 229920005594 polymer fiber Polymers 0.000 abstract description 7
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- -1 hexafluoroisopropenylphthalic acid Chemical compound 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000008064 anhydrides Chemical group 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008041 oiling agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical compound NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 description 1
- ZTLXICJMNFREPA-UHFFFAOYSA-N 3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexaoxonane Chemical compound CC1(C)OOC(C)(C)OOC(C)(C)OO1 ZTLXICJMNFREPA-UHFFFAOYSA-N 0.000 description 1
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 1
- IHZUMPNXUUHJNH-UHFFFAOYSA-N 4-[3,5-bis[4-amino-2-(trifluoromethyl)phenoxy]phenoxy]-3-(trifluoromethyl)aniline Chemical compound FC(C1=C(OC2=CC(=CC(=C2)OC2=C(C=C(C=C2)N)C(F)(F)F)OC2=C(C=C(C=C2)N)C(F)(F)F)C=CC(=C1)N)(F)F IHZUMPNXUUHJNH-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920012306 M5 Rigid-Rod Polymer Fiber Polymers 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
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- 238000005102 attenuated total reflection Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
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- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Artificial Filaments (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides an anti-compression polyimide fiber and a preparation method thereof, wherein the method comprises the following steps: in the synthetic process of polyamide acid, a triamino monomer such as 1,3, 5-tri (4-aminophenoxy) benzene is added to generate a cross-linking structure, and gel is avoided by regulating the synthetic process. Spinning the prepared cross-linked polyamic acid solution into nascent fiber through a wet spinning process, and drying and carrying out gradient heat treatment to obtain the compression-resistant polyimide fiber. The polymer fiber prepared by the method can form a uniform and controllable crosslinking structure, so that the tensile property and the compression resistance of the polymer fiber are obviously improved.
Description
Technical Field
The invention relates to the technical field of polymer fibers, in particular to a polyimide fiber and a preparation method thereof.
Technical Field
Polyimide fiber has high specific strength, high specific modulus, excellent heat resistance, excellent corrosion resistance and other excellent comprehensive properties, and is a great deal of attention in engineering application of composite materials, so that the polyimide fiber is an advanced engineering material with great technical potential. In recent years, with the progress of technology and the large-scale application of composite materials in the fields of aerospace, military industry and civil use, higher and higher requirements are being placed on the performance of the composite materials. In the aspect of mechanical properties, the performance of the material when bearing radial tensile load can be greatly improved by using high-strength high-modulus organic fibers such as PIPD, PBO, aramid fibers and the like as reinforcements. However, the compression resistance of these materials is not satisfactory. The reason for this is that most organic fibers have weak intermolecular forces and only relatively weak van de Waals interactions exist. The low compressive strength also restricts the application of high-strength high-modulus organic fibers including polyimide fibers in the field of composite materials.
In order to improve the compression performance of the organic fiber, the intermolecular force is required to be improved, and specific methods include enhancing intermolecular hydrogen bonding, generating a crosslinked structure, introducing coordination interaction, and the like. Hydrogen gasThe bond action is slightly stronger than van de Waals interaction, but also belongs to one of non-bond actions, and the improvement range of the compression performance of the fiber is limited when the scheme is adopted singly; the fiber is treated at a higher temperature to partially decompose the molecular chains of the fiber to form a crosslinked structure, but this approach, although improving the compression resistance of the fiber, sacrifices the tensile strength of the fiber (W.Sweeny.im.precursors in compressive properties of high modulus fibers by crosslinking [ J)]Journal of Polymer Science Part A Polymer chemistry 1992, vol.30 (No. 6): 1111-1122.). Fe is added to 3+ And Cu 2+ The incorporation of a plasmonic metal ion into a fiber and its coordination reaction with an aromatic heterocycle in the molecular chain may be desirable to enhance its properties, but the influence of a metal ion, particularly a heavy metal ion, on the thermal stability of an aromatic polymer structure. It is generally believed that common heavy metal ions, such as Fe 3+ The polymer is catalyzed to degrade under the high temperature condition, and the aromatic polymer macromolecule fiber usually needs a certain heat treatment to achieve the oriented crystallization on the physical structure (Chinese patent application 201910364958.1, the invention name is a high-performance aromatic polymer fiber and a preparation method).
Disclosure of Invention
Aiming at the defects of insufficient compression resistance and the like of polyimide fibers in the prior art, the invention aims to provide a preparation method of polyimide fibers, which can obviously improve the compression resistance of polyimide fibers. Furthermore, the method can also remarkably improve the tensile property of polyimide fibers.
Another object of the present invention is to provide a polyimide fiber having more excellent tensile properties and compression properties.
In order to achieve the object of the present invention, the present invention provides a method for preparing polyimide fibers, comprising the steps of:
1) Allowing diamine monomer and dianhydride monomer to undergo polycondensation reaction in a reaction solvent to obtain polyamic acid solution;
2) Adding a polyamino compound containing more than 3 amino groups into the polyamic acid solution to perform a crosslinking reaction to obtain a polyamic acid spinning solution, wherein the content of the polyamino compound is 0.5-2% of the total molar amount of the diamine monomer and the dianhydride monomer;
3) Carrying out wet spinning on the polyamic acid spinning solution to obtain polyamic acid precursor;
4) And (3) washing and drying the polyamic acid precursor, and then performing post-treatment to obtain the polyimide fiber, wherein the post-treatment comprises thermal imidization, stretching and heat setting.
According to the invention, the polyimide fiber with a cross-linked structure is prepared by adding the polyfunctional monomer during synthesis, so that the intermolecular acting force of the fiber is greatly enhanced, and the compression resistance of the fiber is improved. Compared with other methods, the method can control the crosslinking density of the intermolecular crosslinking structure more accurately by controlling the content of the polyfunctional monomer, does not need to generate the crosslinking structure through further chemical reaction, does not need to change the main structure of a molecular chain, does not need to introduce metal ions, and can keep the excellent mechanical property and heat resistance of the fiber to the maximum extent. In addition, the method does not need post-treatment on the fiber, and can more conveniently realize integrated continuous production.
Preferably, in the step 1), the solid content of the polyamic acid solution is controlled to be 10-30% in terms of weight percentage concentration, and the molar ratio of the dianhydride monomer to the diamine monomer is 10:9.5-10.
Preferably, in step 1), the dianhydride monomer is one or more selected from the group consisting of 3,3', 4' -benzophenone tetracarboxylic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), pyromellitic dianhydride, 2,3',3,4' -biphenyl tetracarboxylic dianhydride, bisphenol a dianhydride, 4' -oxydiphthalic anhydride, hexafluoroisopropenylphthalic acid, diphenyl sulfide tetracarboxylic dianhydride and 3,3', 4' -diphenyl sulfone tetracarboxylic dianhydride;
the diamine monomer is one or more selected from p-Phenylenediamine (PDA), m-phenylenediamine, 4 '-diaminodiphenyl ether, 2- (4-aminophenyl) -5-aminobenzimidazole (BIA), 4' -diaminodiphenyl sulfone and 4,4 '-diamino-2, 2' -bistrifluoromethyl biphenyl, and more preferably two types;
the reaction solvent is one selected from N, N-dimethylformamide, N-dimethylacetamide, N-vinylpyrrolidone and dimethyl sulfoxide.
Preferably, in step 2), the polyamino compound is one or more selected from 1,3, 5-tris (4-aminophenoxy) benzene (TAPOB), 2,4, 6-Triaminopyrimidine (TAP), 1,3, 5-tris (4-aminophenyl) benzene (TAPB), 2,6,12-triaminetriapterene (TATP) and 1,3, 5-tris (2-trifluoromethyl-4-aminophenoxy) benzene (TFAPOB).
More preferably, in step 1), the dianhydride monomer is 3,3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), and the diamine monomer is p-Phenylenediamine (PDA) and 2- (4-aminophenyl) -5-aminobenzimidazole (BIA), BPDA: PDA: the mole ratio of BIA is 10:1.6 to 2.0:8, more preferably 10:1.8:8, 8; and/or
In step 2), the triamino compound is 1,3, 5-tris (4-aminophenoxy) benzene (TAPOB).
Regarding the reason why the TAPOB effect is preferable, the inventors speculate that: from the molecular structure, the steric hindrance near the amino group of the TAPOB monomer is smaller, the reactivity is higher during synthesis, and meanwhile, the ether bond structure in the molecule can provide certain flexibility for a macromolecular system, so that the molecular chain in the fiber can form a more regular inter-chain stacking structure during heat treatment.
Preferably, in step 3), the wet spinning is: the polyamic acid spinning solution is extruded by a spinneret plate with 100-500 holes and enters a coagulating bath to obtain polyamic acid precursor, wherein the concentration of the coagulating bath is 5-12% in terms of volume fraction, and the spinning operation speed is 0.7-1.2 m/min, and more preferably 0.8-1.1 m/min. The aperture of the spinneret plate is generally 0.04 mm-0.08 mm.
Preferably, in the step 4), the polyamide acid precursor is washed by water, dried at 80-120 ℃, imidized at 240-350 ℃ and finally heat-set at 400-500 ℃ to obtain the fully imidized polyimide fiber.
Preferably, in step 2, the 1,3, 5-tris (4-aminophenoxy) benzene (TAPOB) is dissolved in the reaction solvent and added to the polyamic acid solution at a rate of 4 to 6 seconds/drop.
In order to achieve another object of the present invention, the present invention provides a polyimide fiber having a crosslinked structure, a tensile strength of 2.4 to 3.5GPa, preferably 2.8 to 3.5GPa, more preferably 3.0 to 3.5GPa, and a compressive strength of 550 to 700MPa, preferably 600 to 700MPa, more preferably 650 to 700MPa, prepared by the above method.
The polyimide fiber provided by the invention can be applied to the preparation of various polyimide composite material products, such as radomes, unmanned aerial vehicle shells and the like. Accordingly, the present invention also provides a polyimide composite article comprising the polyimide fibers of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
(1) The multi-functionality monomer is adopted for synthesis, the crosslinking structure inside the fiber can be regulated and controlled by adjusting the monomer proportion, and the crosslinking structure is directly generated during solution synthesis, is less influenced by factors other than the monomer proportion, and is convenient for adjusting the fiber performance.
(2) By means of chemical bonding, acting force among fiber molecular chains is greatly enhanced, and excellent mechanical properties and heat resistance of the fiber can be maintained to the greatest extent while compression resistance of the fiber is enhanced.
(3) The main structure of the molecular chain is not required to be changed, and the hetero atoms are not basically introduced, and meanwhile, extra working procedures are not required to be added in the conventional spinning process, so that the cost is reduced, and the implementation is convenient.
Drawings
FIG. 1 is a schematic illustration of the reaction process of an aromatic polymer fiber prepared according to the present invention.
FIG. 2 is an attenuated total reflection infrared spectrum of an aromatic polymer fiber prepared according to the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the description of the present specification, reference to the term "one embodiment," "another embodiment," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Abbreviations and key terms involved in the present invention are defined as follows: 2- (4-aminophenyl) -5-aminobenzimidazole, i.e., BIA, p-phenylenediamine, i.e., PDA, 3', 4' -biphenyltetracarboxylic dianhydride, i.e., BPDA, dimethylacetamide, i.e., DMAC, and 1,3, 5-tris (4-aminophenoxy) benzene, i.e., TAPOB; in the present invention, as-spun fibers, fibers formed by solidifying a polymer stream extruded from a spinneret in a spinning field are fibers that have not been heat treated yet; the finished fiber is obtained by heat treatment of primary fiber.
Specific embodiments of the present invention are set forth below. The specific method steps of the stretch rebound method used in the examples are as follows: li Menglong, and the tensile resilience method, and the compressive strength [ J ] of carbon fibers, synthetic fiber industry, 2019 (stage 6): 82 to 87.
Example 1
A schematic of the reaction process of the aromatic polymer fibers prepared according to the present invention is shown in FIG. 1. The synthesis is carried out according to the mole ratio of the monomers BPDA to PDA, BIA=10:1.8:8, and the mole ratio of the amino group to the anhydride group is maintained to be 1:1, regulating the solid content of the solution to be 10%, adding all raw materials except a cross-linking agent TAPOB into a reaction kettle and remaining 10ml of DMAc during synthesis, weighing a proper amount of TAPOB to be dissolved in 10ml of DMAc after the solution reacts for 1 hour, wherein the TAPOB content is 1% of the total molar weight of all monomers in the embodiment. The DMAc solution in which TAPOB was dissolved was then withdrawn by a 1ml syringe and slowly added dropwise to the reactor at a rate of about 5 seconds/drop. After about 2/3 of the TAPOB addition, an increase in solution viscosity with the addition of TAPOB was clearly observed, with care being taken that the addition rate was not too fast. Stirring is continued for 0.5 hour after the addition is completed, and then the mixture is transferred to a spinning tank for defoaming.
During spinning, the core layer still contains more solvent after the skin layer is solidified due to the faster solidification rate of the crosslinking system, so that the spinning adopts low spinning speed, small tows and higher concentration of the coagulating bath. In this example, a 120-hole spinneret was used, the coagulation bath concentration was 9%, and the running rate of the filament was 0.96m/min. Because the solvent content in the yarn is high, an oiling agent is needed to prevent the fibers from being adhered. In order to remove the residual solvent in the silk, the fiber is subjected to imidization at 240-350 ℃ after being dried at 80-120 ℃ and finally is subjected to heat setting at 400-500 ℃ to obtain the finished fiber.
The infrared spectrum of the fiber is shown in fig. 2. As shown in FIG. 2, 1228cm of an infrared spectrum (sample name BT-3-01) -1 、1012cm -1 The ether linkage characteristic peak at this point indicates that a crosslinked structure has been incorporated into the polyimide fiber. The polyimide fiber prepared in the embodiment is tested by adopting a YG001A-1 fiber electronic strength tester, the tensile strength of the fiber is measured to be 2.8-3.4 GPa, and the compressive strength of the polyimide prepared by the method is measured by adopting a tensile rebound method to be 556-609 MPa.
Example 2
The synthesis is carried out according to the mole ratio of the monomers BPDA to PDA, BIA=10:1.6:8, and the mole ratio of the amino group to the anhydride group is maintained to be 1:1, regulating the solid content of the solution to be 10%, adding all raw materials except a cross-linking agent TAPOB into a reaction kettle and remaining 10ml of DMAc during synthesis, weighing a proper amount of TAPOB to be dissolved in 10ml of DMAc after the solution reacts for 1 hour, wherein the TAPOB content is 2% of the total molar weight of all monomers in the embodiment. The DMAc solution in which TAPOB was dissolved was then withdrawn by a 1ml syringe and slowly added dropwise to the reactor at a rate of about 5 seconds/drop. After about 2/3 of the TAPOB addition, an increase in solution viscosity with the addition of TAPOB was clearly observed, with care being taken that the addition rate was not too fast. Stirring is continued for 0.5 hour after the addition is completed, and then the mixture is transferred to a spinning tank for defoaming.
During spinning, a 120-hole spinneret plate is adopted, the concentration of a coagulating bath is 9%, and the running speed of a filament is 0.96m/min. Because the solvent content in the yarn is high, an oiling agent is needed to prevent the fibers from being adhered. In order to remove the residual solvent in the silk, the fiber is subjected to imidization at 240-350 ℃ after being dried at 80-120 ℃ and finally is subjected to heat setting at 400-500 ℃ to obtain the finished fiber.
The infrared spectrum of the fiber is shown in fig. 2. As shown in FIG. 2, 1228cm of infrared spectrum (sample name BT-3-02) -1 、1012cm -1 The ether linkage characteristic peak at this point indicates that a crosslinked structure has been incorporated into the polyimide fiber. The polyimide fiber prepared in the embodiment is tested by adopting a YG001A-1 fiber electronic strength tester, the tensile strength of the fiber is measured to be 2.4-2.6 GPa, and the compression strength of the polyimide prepared by the method is measured by adopting a tensile rebound method to be 650-686 MPa.
Comparative example 1
Synthesizing according to the molar ratio of the monomers BPDA to PDA, BIA=10:2:8, and maintaining the molar ratio of the amino groups to the anhydride groups to be 1:1, regulating the solid content of the solution to 10%, and transferring the solution into a spinning tank for defoaming after synthesis.
During spinning, a 120-hole spinneret plate is adopted, the concentration of a coagulating bath is 9%, and the running speed of a filament is 0.96m/min. Drying the fiber at 80-120 ℃, imidizing at 240-350 ℃, and finally heat setting at 400-500 ℃ to obtain the finished fiber.
The infrared spectrum of the fiber is shown in fig. 2. As shown in FIG. 2, 1228cm of infrared spectrum (sample name BT-3-00) -1 、1012cm -1 No characteristic peak of ether bond appears, which indicates that no cross-linked structure is introduced. The polyimide fiber prepared in this example was tested using a YG001A-1 fiber electronic strength tester. The tensile strength of the fiber is measured to be 2.7-3.1 GPa, and the compressive strength of the polyimide prepared by the method is measured to be 240-312 MPa by adopting a tensile rebound method.
From the above results, it can be seen that the compression resistance and the tensile property of the polyimide fiber can be significantly improved by adopting the polyimide wet spinning process disclosed by the invention, and correspondingly, the prepared polyimide fiber has more excellent compression resistance and tensile property.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (13)
1. The preparation method of the polyimide fiber is characterized in that the polyimide fiber has a cross-linked structure, the tensile strength is 2.4 GPa-3.5 GPa, the compressive strength is 550 MPa-700 MPa, and the preparation method of the polyimide fiber comprises the following steps:
1) Allowing diamine monomer and dianhydride monomer to undergo polycondensation reaction in a reaction solvent to obtain polyamic acid solution;
2) Adding a polyamino compound containing more than 3 amino groups into the polyamic acid solution to perform a crosslinking reaction to obtain a polyamic acid spinning solution, wherein the content of the polyamino compound is 0.5-2% of the total molar amount of the diamine monomer and the dianhydride monomer;
3) Carrying out wet spinning on the polyamic acid spinning solution to obtain polyamic acid precursor;
4) Washing and drying the polyamic acid precursor, performing post-treatment to obtain polyimide fiber, wherein the post-treatment comprises thermal imidization, stretching and heat setting,
wherein in the step 1), the dianhydride monomer is 3,3', 4' -biphenyl tetracarboxylic dianhydride, and the diamine monomer is p-phenylenediamine and 2- (4-aminophenyl) -5-aminobenzimidazole, 3', 4' -biphenyl tetracarboxylic dianhydride: p-phenylenediamine: the molar ratio of 2- (4-aminophenyl) -5-aminobenzimidazole is 10:1.6 to 1.8:8, 8;
in step 2), the polyamino compound is 1,3, 5-tris (4-aminophenoxy) benzene.
2. The method according to claim 1, wherein in step 1), the solid content of the polyamic acid solution is controlled to be 10 to 30% in terms of a weight percentage concentration, and the molar ratio of the dianhydride monomer to the diamine monomer is 10:9.5 to 10.
3. The method according to claim 1, wherein in step 1), the reaction solvent is one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-vinylpyrrolidone and dimethylsulfoxide.
4. A process according to claim 3, characterized in that in step 1) the dianhydride monomer is 3,3', 4' -biphenyl tetracarboxylic dianhydride and the diamine monomer is p-phenylenediamine and 2- (4-aminophenyl) -5-aminobenzimidazole, 3', 4' -biphenyl tetracarboxylic dianhydride: p-phenylenediamine: the molar ratio of 2- (4-aminophenyl) -5-aminobenzimidazole is 10:1.8:8.
5. the method according to claim 1, wherein in step 3), the wet spinning is: the polyamic acid spinning solution is extruded by a spinneret plate with 100-500 holes under the drive of high-pressure nitrogen and enters a coagulating bath to obtain polyamic acid precursor, wherein the concentration of the coagulating bath is 5-12%, and the spinning operation speed is 0.7-1.2 m/min.
6. The method according to claim 1, wherein in step 4), the polyamide acid precursor is washed with water, dried at 80 ℃ to 120 ℃, imidized at 240 ℃ to 350 ℃ and finally heat-set at 400 ℃ to 500 ℃ to obtain the fully imidized polyimide fiber.
7. The method according to claim 4, wherein in step 2), the 1,3, 5-tris (4-aminophenoxy) benzene is dissolved in the reaction solvent and added to the polyamic acid solution at a rate of 4 to 6 seconds/drop.
8. The method of claim 1, wherein the tensile strength is 2.8GPa to 3.5GPa and the compressive strength is 600MPa to 700MPa.
9. The method of claim 8, wherein the tensile strength is 3.0-3.5 GPa and the compressive strength is 650-700 MPa.
10. A polyimide fiber prepared by the method of any one of claims 1 to 9, having a crosslinked structure, a tensile strength of 2.4GPa to 3.5GPa, and a compressive strength of 550MPa to 700MPa.
11. The polyimide fiber according to claim 10, wherein the tensile strength is 2.8GPa to 3.5GPa and the compressive strength is 600MPa to 700MPa.
12. The polyimide fiber according to claim 11, wherein the tensile strength is 3.0 to 3.5GPa and the compressive strength is 650 to 700MPa.
13. A polyimide composite article comprising the polyimide fiber of any one of claims 10 to 12.
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| CN111961236A (en) * | 2019-05-20 | 2020-11-20 | 北京化工大学 | Low dielectric polyimide film and preparation method and application thereof |
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| CN105019047A (en) * | 2015-07-16 | 2015-11-04 | 江苏先诺新材料科技有限公司 | Low dielectric polyimide fiber and preparation method thereof |
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