CN106893104B - Diamine compound, polyimide fiber and preparation method thereof - Google Patents
Diamine compound, polyimide fiber and preparation method thereof Download PDFInfo
- Publication number
- CN106893104B CN106893104B CN201710221681.8A CN201710221681A CN106893104B CN 106893104 B CN106893104 B CN 106893104B CN 201710221681 A CN201710221681 A CN 201710221681A CN 106893104 B CN106893104 B CN 106893104B
- Authority
- CN
- China
- Prior art keywords
- polyamic acid
- fiber
- acid solution
- diamine compound
- polyimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 149
- 239000004642 Polyimide Substances 0.000 title claims abstract description 115
- 229920001721 polyimide Polymers 0.000 title claims abstract description 115
- -1 Diamine compound Chemical class 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims description 21
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 79
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 39
- 238000009987 spinning Methods 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000002166 wet spinning Methods 0.000 claims description 21
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 229920002647 polyamide Polymers 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000578 dry spinning Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003880 polar aprotic solvent Substances 0.000 claims description 7
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical class CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 37
- 230000032683 aging Effects 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 24
- 125000001424 substituent group Chemical group 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 230000005855 radiation Effects 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 9
- 238000004088 simulation Methods 0.000 description 9
- 230000003679 aging effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 230000001112 coagulating effect Effects 0.000 description 6
- 150000004985 diamines Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QOLWHUUDSSEZNB-UHFFFAOYSA-N (3,5-dinitrophenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 QOLWHUUDSSEZNB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a diamine compound which has a structure shown in a formula (I). The invention designs a diamine compound with a special structure, and then adopts the diamine compound with the special structure to obtain the polyamic acid solution, thereby improving the structure of the subsequent polyimide, so that the polyimide fiber provided by the invention has excellent atomic oxygen resistance and can resist irradiation and aging.
Description
Technical Field
The invention belongs to the technical field of functional polymer fibers, relates to a diamine compound, a polyimide fiber and a preparation method thereof, and particularly relates to a diamine compound, a polyamic acid solution, an atomic oxygen resistant and irradiation resistant polyimide fiber and a preparation method thereof.
Background
Polyimide is a polymer containing imide ring (-CO-NH-CO-) on the main chain, which has the advantages of high temperature resistance of more than 400 ℃, long-term use temperature range of-200-300 ℃, no obvious melting point, high insulating property, dielectric constant of 4.0 under 1 megahertz, dielectric loss of only 0.004-0.007, strength similar to metal, excellent physical and mechanical properties, excellent electrical properties and chemical stability, is a known organic polymer material with the best comprehensive performance, is positioned at the tip of all polymer materials, is used as a special engineering material, and is widely applied to the fields of aviation, aerospace, microelectronics, nano, liquid crystal, separation membranes, laser and the like at present. Polyimides can be classified into aliphatic, semi-aromatic and aromatic polyimides according to the chemical structure of the repeating unit. According to thermal properties, there are divided into thermoplastic and thermosetting polyimides.
Among polyimide materials in various forms, polyimide fibers are regarded as important, and are also aromatic heterocyclic polymer fibers containing imide rings in molecular chain repeating units, and have excellent properties such as high strength, high modulus, high and low temperature resistance, flame retardance, chemical corrosion resistance and the like. The composite material has been effectively applied to the aspects of high-temperature filter materials, fireproof clothing, explosion-proof clothing, steel-making clothing, radiation protection systems, high-orbit spacecrafts and the like.
With the rapid development of various application fields, the performance requirements of polyimide fibers are increasing, and the requirements of other more excellent properties of polyimide fibers can be expanded are also widely regarded by related researchers. For example, in the low earth orbit application, and in the aerospace device aspect, such as parts of spacecraft, satellites and the like, when the fiber is operated in outer space, the fiber can be subjected to radiation of various rays and atomic oxygen corrosion, the mechanical property of common organic fibers is rapidly reduced after the common organic fibers are subjected to the radiation of the space rays with different energies and the atomic oxygen corrosion, and the mechanical property of the polyimide fiber can also be obviously reduced even though the polyimide fiber is subjected to the ultraviolet and electron beam radiation and the atomic oxygen corrosion in the space environment. Although some prior studies have shown that one of the basic strategies to achieve atomic oxygen resistance in organic materials is to use silicon-containing polymers. Under the condition of atomic oxygen irradiation, the silicon-containing structure on the surface of the material is converted into silicon dioxide, and a dense protective layer is formed on the surface of the material, so that the further occurrence of atomic oxygen degradation can be inhibited. However, when the ultraviolet-ultraviolet. Moreover, the improvement on the organic material is not obvious to the effect of ultraviolet irradiation and electron beam irradiation.
Therefore, how to research and develop a polyimide fiber with radiation resistance and atomic oxygen resistance has become one of the issues of great concern to many prospective researchers in the industry
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a polyimide fiber and a preparation method thereof, and particularly to a polyamic acid solution, and a polyimide fiber with atomic oxygen resistance and radiation resistance and a preparation method thereof. The polyimide fiber provided by the invention can resist space ray irradiation and atomic oxygen corrosion and keep the mechanical property unchanged.
The invention provides a diamine compound, which has a structure shown in a formula (I),
wherein Y is selected from O, S,
POSS has the structure shown in formula (II):
wherein X is- (CH)2)n-，n＝0～6，
R1Is selected from
R2Is composed of
The invention provides a polyamic acid solution, which is obtained by polymerizing a dianhydride compound and a diamine compound;
the diamine compound comprises the diamine compound described in the above technical scheme.
Preferably, the diamine compound further includes one or more of diamine compounds having structures represented by formulas (III-1) to (III-7);
wherein, in the formulas (III-1) to (III-7), D is selected from O, S and-NH-;
e is selected from O, S,
-CH2-、-C(CF3)2-、
The dianhydride compound comprises one or more dianhydride compounds with the structures shown in formulas (IV-1), (IV-2) and (IV-3);
wherein in the formula (IV-3), A is selected from O, S,
-C(CF3)2-、-C(CH3)2-。
Preferably, the molar ratio of the dianhydride compound to the diamine compound is 1: (0.8 to 1.5);
the polymerization is polymerization in a polar aprotic solvent;
the concentration of the polyamic acid solution is 5 wt% -35 wt%.
Preferably, the polar aprotic solvent comprises one or more of N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone;
the polymerization temperature is-10 to 50 ℃.
The invention provides a polyimide fiber, which is obtained by spinning the polyamic acid solution in any one of the technical schemes.
The invention provides a preparation method of polyimide fibers, which comprises the following steps:
1) the polyamic acid solution in any one of the technical schemes is subjected to a wet spinning forming process or a dry spinning forming process to obtain polyamic acid fiber;
2) and (3) imidizing and hot-drawing the polyamide acid fiber obtained in the step to obtain the polyimide fiber.
Preferably, the wet spinning forming process specifically comprises the following steps:
filtering and vacuum defoaming the polyamic acid solution in any one of the technical schemes, spinning, solidifying and forming, and then drafting, washing and drying to obtain polyamic acid fiber;
the solvent for solidification molding is a mixture of a solvent A and a solvent B;
the solvent A comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran;
the solvent B comprises one or more of methanol, ethanol, propanol, isopropanol, glycol, butanol, isobutanol, acetone and butanone.
Preferably, the imidization temperature is 50-550 ℃;
the temperature rise speed of the imidization is 1-30 ℃/min;
the imidization is imidization under vacuum or protective atmosphere.
Preferably, the temperature of the hot drawing is 350-600 ℃;
the drawing multiplying power of the hot drawing is 1-5 times;
the hot drawing is hot drawing under a protective atmosphere.
The invention provides a diamine compound which has a structure shown in a formula (I). The invention also provides a polyamic acid solution, a polyimide fiber and a preparation method thereof. Compared with the prior art, the invention aims at the improvement of the existing organic fiber, can only resist the degradation of atomic oxygen, but has no obvious effect on ultraviolet irradiation and electron beam irradiation. The invention creatively designs a diamine compound with a special structure, and then adopts the diamine compound with the special structure to obtain polyamic acid, thereby improving the structure of polyimide, so that the polyimide fiber provided by the invention has excellent atomic oxygen resistance and can resist irradiation and aging. Experimental results show that the polyimide fiber with a special structure prepared from the diamine compound can resist space ray irradiation and atomic oxygen corrosion in ground simulated irradiation and atomic oxygen tests, and the mechanical property of the polyimide fiber is kept unchanged.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs a purity which is conventional in the field of preparation of analytically pure or polyimide materials.
The invention provides a diamine compound, which has a structure shown in a formula (I),
wherein Y is selected from O, S,
POSS has the structure shown in formula (II):
wherein X is- (CH)2)n-，n＝0～6，
R1Is selected from
R2Is composed of
Said substituent X, Y, R of the invention1And R2The particular elements or structural formulae represented are not particularly required to be represented in a conventional manner well known to those skilled in the art, and the normal meaning can be understood by those skilled in the art based on the general knowledge, and if Y is selected from S, the particular structural formula of formula (I) is preferably:
in the substituent group of X, the value of n is 0-6, more preferably 1-5, more preferably 2-4, and specifically can be 0, 1, 2, 3, 4, 5 or 6.
The substituent Y, POSS, X and R of the invention1And R2In the above formula (I), the position bonded to the general formula (II) is not particularly limited, and may be bonded in a conventional manner known to those skilled in the art, and the present invention has been conventionally described, and if not specifically noted, it is understood that the bond may be bonded to any position in the above substituents, and those skilled in the art can understand its normal meaning based on the general knowledge.
The definition of the POSS in the invention is not particularly limited, and the definition of the POSS known to those skilled in the art can be selected by those skilled in the art according to the actual application situation, the product performance and the quality requirement, and the definition of the POSS in the invention preferably refers to a special class of siloxane polymers, namely cage polysilsesquioxane, abbreviated as POSS, and the main general formula of the POSS can be (RSiO)3/2)nThe molecular structure can be in a trapezoid, branch or lantern structure. The specific structure of the POSS is shown as a formula (II).
The definition and naming of the compound having the structure of formula (I) are not particularly limited in the present invention, and may be defined by the definition and naming methods well known to those skilled in the art, and the compound having the structure of formula (I) provided in the present invention is preferably defined as a diamine compound, and may also be defined as a diamine compound or other compounds, and its naming conforms to the conventional naming method in the art.
The source of the compound having the structure of formula (I) is not particularly limited in the present invention, and the compound can be prepared by conventional methods well known to those skilled in the art, and those skilled in the art can select the compound according to practical application, product performance and quality requirements, and the compound having the structure of formula (I) according to the present invention is preferably synthesized based on conventional synthesis principles, and the specific steps can be selected and adjusted according to the steps in example 1.
The invention provides a polyamic acid solution, which is obtained by polymerizing a dianhydride compound and a diamine compound;
the diamine compound comprises the diamine compound described in the above technical scheme.
The present invention is not particularly limited to other diamine compounds, which may be selected and adjusted by those skilled in the art according to the practical application, product performance and quality requirements, and may be used for preparing polyamic acid, preferably further comprising other diamine compounds or a mixture of diamine compounds, more preferably further comprising one or more diamine compounds having the structures represented by the formulae (III-1) to (III-7), that is, the diamine compound is preferably a diamine compound having a structure represented by formula (I), or a mixture of one or more of a diamine compound having a structure represented by formula (I) and another diamine compound, and more preferably a mixture of one or more of a diamine compound having a structure represented by formula (I) and diamine compounds having structures represented by formulae (III-1) to (III-7).
The diamine compounds having the structures represented by the formulae (III-1) to (III-7) according to the present invention preferably have the following structures:
the present invention is not particularly limited to the specific selection of the substituent represented by D in the above structural formula, and the substituent is the conventional substituent of the above structural formula well known to those skilled in the art, and those skilled in the art can select and adjust the substituent according to the practical application, product performance and quality requirement, and D in the present invention is preferably selected from O, S or-NH-.
The present invention does not require any particular indication of the element or formula represented by the substituent D, and may be represented by conventional indications well known to those skilled in the art, and the ordinary meaning of D can be understood by those skilled in the art based on the general knowledge, and when D is selected from-NH-, the specific formula of formula (III-5) is preferably:
the substituent represented by E in the above structural formula is not particularly limited in the present invention, and may be selected and adjusted by the ordinary substituent of the above structural formula well known to those skilled in the art according to the practical application, product performance and quality requirements, and E in the present invention is preferably selected from O, S,
-CH2-、-C(CF3)2-、
The invention does not require any particular indication of the element or formula represented by the substituent E, and can be represented in a conventional manner well known to those skilled in the art, which would understand its normal meaning based on the general knowledge, e.g., E is selected from
When the formula (III-4) is specified, the structural formula is preferably:
the position of the bond to the general formula in all the substituents D and E is not particularly limited in the present invention, and the bond may be conveniently bonded in a conventional manner well known to those skilled in the art, and the present invention has been conventionally described, and if not specifically noted, it is understood that the bond may be bonded to any position in the above substituents, and those skilled in the art can understand the normal meaning based on the basic common general knowledge.
The dianhydride compound of the present invention is not particularly limited in its selection, and may be selected and adjusted according to practical use, product properties, and quality requirements by those skilled in the art, and preferably includes one or more dianhydride compounds having structures represented by formulae (IV-1), (IV-2), and (IV-3).
The dianhydride compound of the present invention having the structures represented by the formulae (IV-1), (IV-2) and (IV-3) preferably has the following structures:
the substituent represented by A in the structural formula (IV-3) is not particularly limited, and may be selected and adjusted by the skilled person according to the practical application, product performance and quality requirements, and A in the invention is preferably selected from O, S,
-C(CF3)2-or-C (CH)3)2-。
The invention does not require any particular indication of the element or formula represented by the substituent A, and can be represented by conventional indications well known to those skilled in the art, which would understand its normal meaning based on the general knowledge, e.g., A is selected from
When the formula (IV-3) is specifically defined, it is preferable that:
the position of the bond to the general formula in all the substituents A is not particularly limited in the present invention, and the bond may be conveniently bonded in a conventional manner well known to those skilled in the art, and the present invention has been conventionally described, and if not specifically noted, it is understood that the bond may be bonded to any position in the above substituents, and those skilled in the art can understand the normal meaning based on the basic common general knowledge.
The substituent Y, POSS, X and R of the invention1、R2The specific selection of each specific element or structural formula in D, E and a is not particularly limited to a single selection relationship, but may be multiple selection relationships, and conventional selections known to those skilled in the art are sufficient, and the present invention has been described conventionally, and unless otherwise noted, it is understood that one substituted element or structural formula may be specifically selected, and in other cases, a plurality of different elements or structural formulas may be selected simultaneously, or a mixture of different compounds consisting of single or multiple substituted elements or structural formulas may be used.
The molar ratio of the dianhydride compound to the diamine compound is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to the actual application, product properties and quality requirements, and may be selected and adjusted according to the conventional addition ratio for preparing polyamic acid solution, which is well known to those skilled in the art, and the molar ratio of the dianhydride compound to the diamine compound of the present invention is preferably 1: (0.8 to 1.5), more preferably 1: (0.9 to 1.4), more preferably 1: (1.0 to 1.3), most preferably 1: (1.1-1.2).
The medium for the polymerization is not particularly limited in the present invention, and may be a solvent for preparing a polyamic acid solution, which is well known to those skilled in the art, and can be selected and adjusted according to the actual application, product properties, and quality requirements, and the polymerization in the present invention is preferably performed in a polar aprotic solvent, and the polar aprotic solvent preferably specifically includes one or more of N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone, more preferably N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, or N-methylpyrrolidone, and most preferably N, N-dimethylacetamide or N, N-dimethylformamide.
The amount of the polar aprotic solvent used is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to the practical application, product performance and quality requirements, and the concentration of the polyamic acid solution, i.e. the polyamic acid solution, is preferably 5 wt% to 35 wt%, more preferably 10 wt% to 30 wt%, and most preferably 15 wt% to 25 wt%, in order to facilitate the subsequent preparation of polyimide and the spinning molding process.
The polymerization temperature is not particularly limited in the present invention, and the temperature for preparing the polyamic acid solution known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual application, product performance and quality requirements, and the polymerization temperature in the present invention is preferably-10 to 50 ℃, more preferably 0 to 40 ℃, more preferably 10 to 30 ℃, and most preferably 15 to 25 ℃. The polymerization time is not particularly limited in the present invention, and the time for preparing the polyamic acid solution is known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application, product properties, and quality requirements.
The invention provides a polyimide fiber, which is obtained by spinning the polyamic acid solution in any one of the technical schemes.
The spinning process or other processes for preparing polyimide fibers are not particularly limited in the present invention, and may be any processes for preparing polyimide fibers known to those skilled in the art, and those skilled in the art can select and adjust the processes according to the actual application, product performance and quality requirements.
In order to ensure the performance of the polyimide fiber and clearly describe the overall technical scheme, the invention also provides a preparation method of the polyimide fiber, which comprises the following steps:
1) the polyamic acid solution in any one of the technical schemes is subjected to a wet spinning forming process or a dry spinning forming process to obtain polyamic acid fiber;
2) and (3) imidizing and hot-drawing the polyamide acid fiber obtained in the step to obtain the polyimide fiber.
Firstly, carrying out a wet spinning forming process or a dry spinning forming process on a polyamic acid solution (polyamic acid solution) in any one of the technical schemes to obtain a polyamic acid fiber;
the concentration of the polyamic acid solution is not particularly limited in the present invention, and may be the concentration of the conventional raw material for preparing polyimide fiber, which is well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to the actual production situation, product performance and quality requirements, and the concentration of the polyamic acid solution in the present invention is preferably 5 wt% to 35 wt%, more preferably 10 wt% to 30 wt%, and most preferably 15 wt% to 25 wt%.
The polyamic acid solution is not particularly limited, and may be prepared by conventional conditions of the polyamic acid solution for preparing polyimide fiber, which are well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, product performance and quality requirements.
The specific steps and parameters of the filtration and vacuum deaeration are not particularly limited in the present invention, and the pretreatment step of the polyamic acid solution and the corresponding conditions in the preparation of the polyimide fiber, which are well known to those skilled in the art, may be selected and adjusted by those skilled in the art according to the actual production conditions, product performance and quality requirements.
The invention has no particular limitation on the specific process of the wet spinning forming process, and only needs the wet spinning forming process for preparing the polyimide fiber, which is well known to the technicians in the field, and the technicians in the field can select and adjust the wet spinning forming process according to the actual production condition, the product performance and the quality requirement, in order to improve the integrity of the whole process and the product performance, the specific steps of the wet spinning forming process are preferably as follows:
filtering and vacuum defoaming the polyamic acid solution, spinning, solidifying and forming, drafting, washing and drying to obtain the polyamic acid fiber.
More specifically, it is preferable that:
filtering the polyamic acid spinning solution, defoaming in vacuum, extruding the solution through a metering pump from a spinneret orifice, forming the solution in a coagulating bath, drafting, washing with water, and drying through a channel to obtain the polyamic acid fiber.
The solvent used for the coagulation forming in the present invention is not particularly limited, and may be a solvent for a coagulation bath of a wet spinning forming process well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, product performance and quality requirements, and the solvent for the coagulation forming in the present invention is preferably a mixture of solvent a and solvent B, that is, preferably a mixture of two solvents.
The specific selection of the solvent a and the solvent B is not particularly limited in the present invention, and may be a solvent for a coagulation bath in a wet spinning molding process well known to those skilled in the art, and those skilled in the art may select and adjust the solvent according to actual production conditions, product properties, and quality requirements, and the solvent a of the present invention preferably includes one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and tetrahydrofuran, and more preferably, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, or tetrahydrofuran. The solvent B of the present invention preferably includes one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol, butanol, isobutanol, acetone, and butanone, and more preferably methanol, ethanol, propanol, isopropanol, ethylene glycol, butanol, isobutanol, acetone, or butanone.
The specific addition amount of the solvent A and the solvent B is not particularly limited in the present invention, and can be selected and adjusted by those skilled in the art according to the actual production situation, the product performance and the quality requirement. The present invention has no particular limitation on other process parameters of the wet spinning forming process steps, and the conventional process parameters of the wet spinning forming process for preparing polyimide fibers, which are well known to those skilled in the art, can be selected and adjusted by those skilled in the art according to actual production conditions, product performance and quality requirements.
The invention has no particular limitation on the specific process of the dry spinning forming process, and only needs the wet spinning forming process for preparing the polyimide fiber, which is well known to the technicians in the field, and the technicians in the field can select and adjust the wet spinning forming process according to the actual production condition, the product performance and the quality requirement, in order to improve the integrity of the whole process and the product performance, the specific steps of the dry spinning forming process are preferably as follows:
filtering and vacuum defoaming the polyamic acid solution, spinning, and directly thermoforming to obtain the polyamic acid fiber.
More specifically, it is preferable that:
filtering the polyamic acid spinning solution in any one of the technical schemes, defoaming in vacuum, extruding the solution by a spinneret plate through a metering pump, and forming through a hot air channel to obtain the polyamic acid fiber.
The present invention has no particular limitation on the specific steps and process parameters of the dry spinning forming process, and the conventional steps and parameters of the dry spinning forming process for preparing polyimide fibers, which are well known to those skilled in the art, can be selected and adjusted by those skilled in the art according to actual production conditions, product performance and quality requirements.
The polyamide acid fiber obtained in the step is imidized and thermally drawn to obtain the polyimide fiber.
The imidization (thermal imidization) temperature is not particularly limited in the present invention, and the imidization temperature of the polyamic acid known to those skilled in the art can be selected and adjusted according to the actual application, product performance and quality requirements, and the imidization temperature in the present invention is preferably 50 to 550 ℃, more preferably 100 to 500 ℃, more preferably 200 to 400 ℃, and most preferably 250 to 350 ℃.
The temperature rise rate of the imidization is not particularly limited, and can be selected and adjusted by the skilled in the art according to the actual application condition, product performance and quality requirements, and the temperature rise rate of the imidization is preferably 1-30 ℃/min, more preferably 5-25 ℃/min, more preferably 10-20 ℃/min, and most preferably 13-17 ℃/min.
The equipment for imidization is not particularly limited in the present invention, and may be equipment for imidizing polyamic acid, which is well known to those skilled in the art, and can be selected and adjusted according to the practical application, product performance and quality requirements.
The time for the imidization is not particularly limited in the present invention, and the time for preparing polyamic acid for imidization, which is well known to those skilled in the art, can be selected and adjusted by those skilled in the art according to the practical application, product performance and quality requirements. The other conditions for the imidization are not particularly limited in the present invention, and may be conventional conditions for preparing polyamic acid imidization well known to those skilled in the art, and those skilled in the art may select and adjust according to the actual application, product performance and quality requirements, and the imidization in the present invention is preferably imidized under vacuum or protective atmosphere, more preferably under vacuum, nitrogen or protective atmosphere, and more preferably under vacuum, nitrogen or argon.
The temperature of the hot drawing is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to the actual application, product performance and quality requirements, and is preferably 350 to 600 ℃, more preferably 400 to 550 ℃, and most preferably 450 to 500 ℃.
The draft magnification of the hot draft is not particularly limited, and the draft magnification of the hot draft known to a person skilled in the art can be selected and adjusted by the person skilled in the art according to the actual application condition, the product performance and the quality requirement, and the draft magnification of the hot draft is preferably 1 to 5 times, more preferably 1.5 to 4.5 times, more preferably 2 to 4 times, and most preferably 2.5 to 3.5 times.
The hot drawing time is not particularly limited in the present invention, and can be selected and adjusted by those skilled in the art according to the actual application, product performance and quality requirements. The other conditions of the hot drawing are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to the practical application, product properties and quality requirements, as the conditions of the hot drawing for preparing the polyimide fiber are well known to those skilled in the art, and the hot drawing is preferably performed under a protective atmosphere, more preferably under nitrogen or a protective atmosphere, and more preferably under nitrogen or argon.
The invention provides a diamine compound, a polyamic acid solution, a polyimide fiber and a preparation method thereof, the invention designs a diamine compound with a special structure, further improves polyamic acid, and finally obtains a novel polyimide structure, a spinning solution is prepared by creatively adopting a diamine monomer with a special structure and copolymerizing with a conventional dianhydride monomer or a conventional diamine and dianhydride monomer, a wet spinning process is adopted in a specific coagulating bath to prepare the polyamic acid fiber, the polyamic acid fiber is thermally imidized, and finally the polyimide fiber with excellent atomic oxygen resistance and radiation aging resistance is obtained through thermal drafting. The preparation of the irradiation-resistant and atomic oxygen-resistant polyamic acid spinning solution, the spinning of the polyamic acid fiber, the imidization of the polyamic acid fiber and the hot drawing of the polyimide fiber obtain the polyimide fiber which has excellent atomic oxygen resistance and can resist irradiation aging, and the polyimide fiber is more suitable for being applied to the technical fields of aviation, aerospace, outer space application and the like.
Experimental results show that the polyimide fiber with a special structure prepared from the polyamic acid solution can resist space ray irradiation and atomic oxygen corrosion in ground simulation irradiation and atomic oxygen tests, and the mechanical property of the polyimide fiber is kept unchanged.
For further illustration of the present invention, the following will describe a polyimide fiber and its preparation method in detail with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given, only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
The present invention is not particularly limited with respect to the sources of the raw materials in the following examples, and they may be prepared by a preparation method known to those skilled in the art or commercially available.
Example 1
Preparation of 3- [4- (POSS-methylene-oxy) benzoyl ] -1, 5-diaminobenzene
The synthetic route is shown as the following formula:
1) and 3- [4- (POSS-methylene-oxy) benzoyl ] -1, 5-dinitrobenzene synthesis:
to the reaction vessel were added A, 3- (4-hydroxybenzoyl) -1, 5-dinitrobenzene (2.882g, 0.01mol), monochloromethylPOSS (10.82g, 0.01mol) and 100ml tetrahydrofuran. Stirred at room temperature and dissolved. Sodium hydride (0.288g, 0.012mol) was added portionwise. The reaction was continued for 6 hours. The reaction mixture was poured into 250ml of water, and a white solid was precipitated, filtered and dried under vacuum at room temperature.
9.8g of product was finally obtained, with a calculated yield of 73.4%. The nuclear magnetism characterization is carried out on the 3- [4- (POSS-methylene-oxy) -benzoyl ] -1, 5-dinitrobenzene prepared by the steps. Nuclear magnetic hydrogen spectrum data are as follows:
1H NMR(DMSO，300MHz)δ9.25(s，1H)，8.92(s，2H)，7.85(d，2H)，7.79(m，16H)，7.47(m，7H)，7.40(m，16H)，7.05(d，2H)，4.20(s，2H)。
2) 3- [4- (POSS-methylene-oxy) benzoyl ] -1, 5-diaminobenzene:
to a 200ml high pressure reaction vessel were charged B, 3- [4- (POSS-methylene-oxy) -benzoyl ] -1, 5-dinitrobenzene (5.00g, 0.0037mol), palladium on carbon (0.05g) and 80ml THF under a hydrogen pressure of 2.0 MPa. The reaction was carried out at room temperature for 8 hours. After the palladium-carbon is filtered, the reaction solution is concentrated, solid is precipitated and filtered.
4.10g of product is finally obtained, with a calculated yield of 85.1%. The nuclear magnetism characterization is carried out on the 3- [4- (POSS-methylene-oxy) benzoyl ] -1, 5-diaminobenzene prepared by the steps. Nuclear magnetic hydrogen spectrum data are as follows:
1H NMR(DMSO，300MHz)7.80(d，2H)，δ7.79(m，16H)，7.47(m，7H)，7.40(m，16H)，7.05(d，2H)，δ6.27(s，1H)，6.00(s，2H)，5.00(s，4H)，4.20(s，2H)。
preparation of polyimide fibers
637.40g (0.5mol) of 3- [4- (POSS-methylene-oxy) benzoyl ] -1, 5-diaminobenzene prepared in the above step and 100.12g (0.5mol) of 4, 4' -diphenylether diamine were dissolved in 3500ml of N, N-dimethylformamide, 218.21g (1.0mol) of pyromellitic dianhydride was added under stirring, and reacted at 30 ℃ for 24 hours to obtain a viscous polyamic acid spinning solution which was directly used as a spinning dope after filtration.
The polyamic acid slurry is spun and formed by adopting a dry-jet wet spinning technical route, the normal-temperature spinning slurry is accurately metered by a metering pump, and then is extruded out of a spinneret orifice and enters a coagulating bath of N, N-dimethylformamide and water (the volume ratio is 1: 2) through an air layer. The spinneret plate has 30 holes, the aperture phi is 0.12mm, the spray-draw ratio is 3.0 times, the spinning speed is 50m/min, and the height of the air layer is 15 mm. Washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain the polyamide acid fiber.
And treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber. The thermal imidization temperature is 50-300 ℃, and the heating rate is 2 ℃/min. The obtained polyimide fiber is drafted by 1.5 times at 450 ℃ in a nitrogen environment to obtain the polyimide finished product fiber.
The polyimide fiber prepared in example 1 of the present invention was subjected to a performance test.
The breaking strength of the fiber is 0.75GPa, the modulus is 5.80GPa, and the breaking elongation is 12.5%.
The schematic molecular structural formula of the polyimide fiber in this example is as follows:
the polyimide fiber prepared in example 1 of the present invention was subjected to a ground-based irradiation simulation and an atomic oxygen test to test aging properties.
Referring to table 1, table 1 shows the mechanical properties of the polyimide fiber prepared in example 1 of the present invention and the polyimide fiber prepared in comparative example 1 after aging with the same dosage of atomic oxygen and radiation.
Comparative example 1
200.24g (1mol) of 4, 4' -diphenyl ether diamine was dissolved in 3500ml of N, N-dimethylformamide, 218.21g (1.0mol) of pyromellitic dianhydride was added under stirring, and reacted at 30 ℃ for 24 hours to give a pale yellow and viscous polyamic acid spinning solution, which was filtered and used as a spinning dope.
The polyamic acid slurry was spun, imidized and drawn by heat in the same manner as in example 1 to obtain a polyimide fiber.
The polyimide fiber prepared in comparative example 1 of the present invention was subjected to a performance test.
The breaking strength of the fiber is 0.78GPa, the modulus is 6.52GPa, and the breaking elongation is 10.8%.
The molecular structural formula of the polyimide fiber in this comparative example is as follows:
the polyimide fiber prepared in comparative example 1 of the present invention was subjected to a ground-based irradiation simulation and an atomic oxygen test to test aging properties.
Referring to table 1, table 1 shows the mechanical properties of the polyimide fiber prepared in example 1 of the present invention and the polyimide fiber prepared in comparative example 1 after aging with the same dosage of atomic oxygen and radiation.
TABLE 1
Example 2
637.40g (0.5mol) of 3- [4- (POSS-methylene-oxy) benzoyl ] -1, 5-diaminobenzene and 54.07g (0.5mol) of p-phenylenediamine were dissolved in 3500ml of N, N-dimethylacetamide, and 294.23g (1mol) of 4, 4' -biphenyldianhydride was added under stirring to react at 30 ℃ for 24 hours to obtain a pale yellow viscous polyamic acid spinning solution, which was filtered and used as a spinning dope.
The polyamic acid slurry is spun and formed by adopting a dry-jet wet spinning technical route, the normal-temperature spinning slurry is accurately metered by a metering pump, and then is extruded out of a spinneret orifice and enters a coagulating bath of N, N-dimethylformamide and water (the volume ratio is 1: 3) through an air layer. The spinneret plate has 30 holes, the aperture phi is 0.12mm, the spray-draw ratio is 2.5 times, the spinning speed is 40m/min, and the height of the air layer is 15 mm. Washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain the polyamide acid fiber.
And treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber. The thermal imidization temperature is 50-350 ℃, and the heating speed is 2 ℃/min. The obtained polyimide fiber is drafted by 1.5 times at 480 ℃ in a nitrogen environment to obtain the polyimide finished product fiber.
The polyimide fiber prepared in example 2 of the present invention was subjected to a performance test.
The breaking strength of the fiber is 1.38GPa, the modulus is 14.52GPa, and the breaking elongation is 5.8%.
The schematic molecular structural formula of the polyimide fiber in this example is as follows:
the polyimide fiber prepared in example 2 of the present invention was subjected to a ground-based irradiation simulation and an atomic oxygen test to test aging properties.
Referring to table 2, table 2 shows the mechanical properties of the polyimide fibers prepared in example 2 of the present invention and the polyimide fibers prepared in comparative example 2 after aging with the same dosage of atomic oxygen and radiation.
Comparative example 2
108.14g (1mol) of p-phenylenediamine is dissolved in 3500ml of N, N-dimethylacetamide, 294.23g (1mol) of 4, 4' -biphenyl dianhydride is added under stirring, reaction is carried out for 24 hours at 30 ℃ to obtain light yellow viscous polyamic acid spinning solution, and the solution is directly used as spinning slurry after being filtered.
The polyamic acid slurry was spun, imidized and drawn by heat in the same manner as in example 2 to obtain a polyimide fiber.
The polyimide fiber prepared in comparative example 2 of the present invention was subjected to a performance test.
The breaking strength of the fiber is 1.45GPa, the modulus is 15.88GPa, and the breaking elongation is 4.5%.
The schematic molecular structural formula of the polyimide fiber in this comparative example is as follows:
the polyimide fiber prepared in comparative example 2 of the present invention was subjected to a ground-based irradiation simulation and an atomic oxygen test to test aging properties.
Referring to table 2, table 2 shows the mechanical properties of the polyimide fibers prepared in example 2 of the present invention and the polyimide fibers prepared in comparative example 2 after aging with the same dosage of atomic oxygen and radiation.
TABLE 2
Example 3
637.40g (0.5mol) of 3- [4- (POSS-methylene-oxy) benzoyl ] -1, 5-diaminobenzene and 100.12g (0.5mol) of 4, 4' -diphenylether diamine were dissolved in 3500ml of N, N-dimethylformamide, and 218.21g (1.0mol) of pyromellitic dianhydride was added under stirring to react at 30 ℃ for 24 hours to give a pale yellow and viscous polyamic acid spinning solution, which was filtered and used as a spinning dope.
The polyamic acid slurry is spun and formed by adopting a dry-jet wet spinning technical route, the normal-temperature spinning slurry is accurately metered by a metering pump, and then is extruded out of a spinneret orifice and enters a coagulating bath of N, N-dimethylformamide and water (the volume ratio is 1: 2) through an air layer. The spinneret plate has 30 holes, the aperture phi is 0.12mm, the spray-draw ratio is 3.0 times, the spinning speed is 50m/min, and the height of the air layer is 15 mm. Washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain the polyamide acid fiber.
And treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber. The thermal imidization temperature is 50-300 ℃, and the heating speed is 2 ℃/min. The obtained polyimide fiber is drafted by 1.5 times at 450 ℃ in a nitrogen environment to obtain the polyimide finished product fiber.
The polyimide fiber prepared in example 3 of the present invention was subjected to a performance test.
The breaking strength of the fiber is 0.75GPa, the modulus is 5.80GPa, and the breaking elongation is 12.5%.
The schematic molecular structural formula of the polyimide fiber in this example is as follows:
the polyimide fiber prepared in example 3 of the present invention was subjected to a ground-based irradiation simulation and an atomic oxygen test to test aging properties.
Referring to table 3, table 3 shows the mechanical properties of the polyimide fibers prepared in example 3 of the present invention and the polyimide fibers prepared in comparative example 3 after aging with the same dosage of atomic oxygen and radiation.
Comparative example 3
200.24g (1mol) of 4, 4' -diphenyl ether diamine was dissolved in 3500ml of N, N-dimethylformamide, 218.21g (1.0mol) of pyromellitic dianhydride was added under stirring, and reacted at 30 ℃ for 24 hours to give a pale yellow and viscous polyamic acid spinning solution, which was filtered and used as a spinning dope.
The polyamic acid slurry was spun, imidized and drawn by heat in the same manner as in example 1 to obtain a polyimide fiber.
The polyimide fiber prepared in comparative example 3 of the present invention was subjected to a performance test.
The breaking strength of the fiber is 0.78GPa, the modulus is 6.52GPa, and the breaking elongation is 10.8%.
The schematic molecular structural formula of the polyimide fiber in this comparative example is as follows:
the polyimide fiber prepared in comparative example 3 of the present invention was subjected to a ground-based irradiation simulation and an atomic oxygen test to test aging properties.
Referring to table 3, table 3 shows the mechanical properties of the polyimide fibers prepared in example 3 of the present invention and the polyimide fibers prepared in comparative example 3 after aging with the same dosage of atomic oxygen and radiation.
TABLE 3
Example 4
Preparation of 3- [4- (POSS-methylthio) benzoyl ] -1, 5-diaminobenzene
Synthetic route reference is made to example 1
638.42g (0.5mol) of 3- [4- (POSS-methylthio) benzoyl ] -1, 5-diaminobenzene prepared in the above step and 54.07g (0.5mol) of p-phenylenediamine were dissolved in 3500ml of N, N-dimethylacetamide, and 294.23g (1mol) of 4, 4' -biphenyldianhydride was added under stirring to react at 30 ℃ for 24 hours to obtain a pale yellow viscous polyamic acid spinning solution, which was filtered and used as a spinning dope directly.
The polyamic acid slurry is spun and formed by adopting a dry-jet wet spinning technical route, the normal-temperature spinning slurry is accurately metered by a metering pump, and then is extruded out of a spinneret orifice and enters a coagulating bath of N, N-dimethylformamide and water (1: 3.5 volume ratio) through an air layer. The spinneret plate has 30 holes, the aperture phi is 0.12mm, the spray-draw ratio is 2.5 times, the spinning speed is 40m/min, and the height of the air layer is 15 mm. Washing the nascent fiber with water, and drying by a hot nitrogen channel to obtain the polyamide acid fiber.
And treating the polyamide acid fiber in a nitrogen environment by a gradient heating thermal imidization furnace to obtain the polyimide fiber. The thermal imidization temperature is 50-350 ℃, and the heating speed is 2 ℃/min. The obtained polyimide fiber is drafted by 1.5 times at 480 ℃ in a nitrogen environment to obtain the polyimide finished product fiber.
The polyimide fiber prepared in example 4 of the present invention was subjected to a performance test.
The breaking strength of the fiber is 1.05GPa, the modulus is 9.55GPa, and the breaking elongation is 7.5%.
The schematic molecular structural formula of the polyimide fiber in this example is as follows:
the polyimide fiber prepared in example 4 of the present invention was subjected to a ground-based irradiation simulation and an atomic oxygen test to test aging properties.
Referring to table 4, table 4 shows the mechanical properties of the polyimide fibers prepared in example 4 of the present invention and the polyimide fibers prepared in comparative example 4 after aging with the same dosage of atomic oxygen and radiation.
Comparative example 4
108.14g (1mol) of p-phenylenediamine is dissolved in 3500ml of N, N-dimethylacetamide, 294.23g (1mol) of 4, 4' -biphenyl dianhydride is added under stirring, reaction is carried out for 24 hours at 30 ℃ to obtain light yellow viscous polyamic acid spinning solution, and the solution is directly used as spinning slurry after being filtered.
The polyamic acid slurry was spun, imidized and drawn by heat in the same manner as in example 4 to obtain a polyimide fiber.
The polyimide fiber prepared in comparative example 4 of the present invention was subjected to a performance test.
The breaking strength of the fiber is 1.45GPa, the modulus is 15.88GPa, and the breaking elongation is 4.5%.
The schematic molecular structural formula of the polyimide fiber in this comparative example is as follows:
the polyimide fiber prepared in comparative example 4 of the present invention was subjected to a ground-based irradiation simulation and an atomic oxygen test to test aging properties.
Referring to table 4, table 4 shows the mechanical properties of the polyimide fibers prepared in example 4 of the present invention and the polyimide fibers prepared in comparative example 4 after aging with the same dosage of atomic oxygen and radiation.
TABLE 4
While the present invention has been described in detail with respect to a diamine compound, a polyamic acid solution, and atomic oxygen and radiation resistant polyimide fibers and methods of making the same, specific examples are set forth herein to provide an understanding of the principles and embodiments of the present invention, and are presented to aid in understanding the principles of the present invention and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A diamine compound characterized by having the structure of formula (I),
wherein Y is selected from O, S,
POSS has the structure shown in formula (II):
wherein X is- (CH)2)n-，n＝0～6，
R1Is selected from
R2Is composed of
2. A polyamic acid solution is characterized in that the polyamic acid solution is obtained by polymerizing a dianhydride compound and a diamine compound;
the diamine compound comprises the diamine compound of claim 1.
3. The polyamic acid solution according to claim 2, wherein the diamine compound further comprises one or more of diamine compounds having structures represented by formulas (III-1) to (III-7);
wherein, in the formulas (III-1) to (III-7), D is selected from O, S and-NH-;
e is selected from O, S,
-CH2-、-C(CF3)2-、
The dianhydride compound comprises one or more dianhydride compounds with the structures shown in formulas (IV-1), (IV-2) and (IV-3);
wherein in the formula (IV-3), A is selected from O, S,
-C(CF3)2-、-C(CH3)2-。
4. The polyamic acid solution according to claim 2, wherein the molar ratio of the dianhydride compound and the diamine compound is 1: (0.8 to 1.5);
the polymerization is polymerization in a polar aprotic solvent;
the concentration of the polyamic acid solution is 5 wt% -35 wt%.
5. The polyamic acid solution of claim 4, wherein said polar aprotic solvent comprises one or more of N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidinone;
the polymerization temperature is-10 to 50 ℃.
6. A polyimide fiber obtained by spinning the polyamic acid solution according to any one of claims 2 to 5.
7. The preparation method of the polyimide fiber is characterized by comprising the following steps:
1) subjecting the polyamic acid solution of any one of claims 2-5 to a wet spinning forming process or a dry spinning forming process to obtain polyamic acid fiber;
2) and (3) imidizing and hot-drawing the polyamide acid fiber obtained in the step to obtain the polyimide fiber.
8. The preparation method according to claim 7, wherein the wet spinning forming process specifically comprises the following steps:
filtering and vacuum defoaming the polyamic acid solution as claimed in any one of claims 2 to 5, spinning, solidifying and forming, drafting, washing with water and drying to obtain polyamic acid fiber;
the solvent for solidification molding is a mixture of a solvent A and a solvent B;
the solvent A comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and tetrahydrofuran;
the solvent B comprises one or more of methanol, ethanol, propanol, isopropanol, glycol, butanol, isobutanol, acetone and butanone.
9. The method according to claim 7, wherein the imidization temperature is 50 to 550 ℃;
the temperature rise speed of the imidization is 1-30 ℃/min;
the imidization is imidization under vacuum or protective atmosphere.
10. The method according to claim 7, wherein the temperature of the hot drawing is 350 to 600 ℃;
the drawing multiplying power of the hot drawing is 1-5 times;
the hot drawing is hot drawing under a protective atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710221681.8A CN106893104B (en) | 2017-04-06 | 2017-04-06 | Diamine compound, polyimide fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710221681.8A CN106893104B (en) | 2017-04-06 | 2017-04-06 | Diamine compound, polyimide fiber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106893104A CN106893104A (en) | 2017-06-27 |
| CN106893104B true CN106893104B (en) | 2020-07-07 |
Family
ID=59193230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710221681.8A Active CN106893104B (en) | 2017-04-06 | 2017-04-06 | Diamine compound, polyimide fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106893104B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791833B (en) * | 2019-11-26 | 2021-02-05 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005232024A (en) * | 2004-02-17 | 2005-09-02 | Chisso Corp | Diamine having silsesquioxane skeleton and polymer using the same |
| US9006371B1 (en) * | 2010-09-28 | 2015-04-14 | United States Of America As Represented By The Secretary Of The Navy | Synthesis of oligomeric silsesquioxane monomers for high performance polymers |
| CN105297165A (en) * | 2015-11-17 | 2016-02-03 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
-
2017
- 2017-04-06 CN CN201710221681.8A patent/CN106893104B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005232024A (en) * | 2004-02-17 | 2005-09-02 | Chisso Corp | Diamine having silsesquioxane skeleton and polymer using the same |
| US9006371B1 (en) * | 2010-09-28 | 2015-04-14 | United States Of America As Represented By The Secretary Of The Navy | Synthesis of oligomeric silsesquioxane monomers for high performance polymers |
| CN105297165A (en) * | 2015-11-17 | 2016-02-03 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Atomic Oxygen Effects on POSS Polyimides in Low Earth Orbit";Timothy K. Minton, et al.;《lied Materials & Interfaces》;20111221;第4卷;第492-502页 * |
| Timothy K. Minton, et al.."Atomic Oxygen Effects on POSS Polyimides in Low Earth Orbit".《lied Materials & Interfaces》.2011,第4卷 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106893104A (en) | 2017-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101385279B1 (en) | Asymmetric diamine compounds containing two functional groups, and polymers therefrom | |
| US9011739B2 (en) | Methods of continuously manufacturing polymide fibers | |
| EP3378977B1 (en) | Polyimide fiber and preparation method therefor | |
| CN110791833B (en) | Polyimide fiber and preparation method thereof | |
| CN104928790A (en) | Method for preparing polyimide fibers | |
| CN101007778A (en) | Chain-prolonged type fluorenyl bimaleimide and its preparation method | |
| CN111040164B (en) | Colorless transparent non-fluorine polyimide film with low thermal expansion coefficient and preparation method and application thereof | |
| CN103696033A (en) | Preparation method of polyimide fiber | |
| WO2018072291A1 (en) | Selenium-containing polyimide polymer and preparation method therefor and use thereof | |
| CN111041589B (en) | Preparation method of polyimide aerogel fiber | |
| Zhang et al. | Heat-resistant polybenzoxazole nanofibers made by electrospinning | |
| CN115403764B (en) | Polyaryletherketone compound containing epoxy group and preparation method thereof | |
| CN109666979B (en) | Preparation method of polyimide nanofiber | |
| CN106893104B (en) | Diamine compound, polyimide fiber and preparation method thereof | |
| EP3378976B1 (en) | Polyimide fiber and preparation method therefor | |
| CN104947228A (en) | Polyimide fiber and preparation method thereof | |
| CN109666171B (en) | Preparation method of uniform polyimide film | |
| KR100205962B1 (en) | Novel soluble polyimide resin | |
| CN110863258B (en) | Polyimide fiber and preparation method thereof | |
| JP6289015B2 (en) | Polyimide fiber and method for producing polyimide fiber | |
| Xu et al. | Synthesis of soluble and thermally stable poly (N‐arylenebenzimidazole) s | |
| JP6289014B2 (en) | Polyimide fibers and assemblies | |
| KR101652699B1 (en) | Polyhydroxyamides substituted flruoro-substituents and method for preparing of the same | |
| CN111057238B (en) | Polyimide precursor composition and preparation method and application thereof | |
| CN108997580B (en) | Polyether imide containing anthrone and trifluoromethyl structures and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |