CN104499085A - Method for improving strength, modulus, thermal stability and water resistance of polyimide fiber - Google Patents

Method for improving strength, modulus, thermal stability and water resistance of polyimide fiber Download PDF

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CN104499085A
CN104499085A CN201410664198.3A CN201410664198A CN104499085A CN 104499085 A CN104499085 A CN 104499085A CN 201410664198 A CN201410664198 A CN 201410664198A CN 104499085 A CN104499085 A CN 104499085A
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modulus
fiber
sio
polyimide fiber
wet
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CN104499085B (en
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景晓辉
丁欣宇
蔡卫
程海军
龚磊
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Nantong University
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    • 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
    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/04—Dry spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

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  • Mechanical Engineering (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Artificial Filaments (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention provides a method for improving the strength, modulus, thermal stability and water resistance of polyimide fiber. Surface modified nano silica is added to the polyimide fiber, and hybrid of silica with polyimide, spinning and wet drawing, thermal imidization and hot stretching treatment are conducted to effectively improve the strength, modulus, thermal stability and water resistance of polyimide fiber. The method of the invention has the advantages of simple operation, low cost and obvious effect, is applicable to polyimide fiber prepared from all kinds of diamine and dianhydride monomers, and overcomes the performance defects of single material fiber and conventional composite material fiber; and the prepared polyimide fiber has both the advantages of organic materials and inorganic materials, and can be widely used in the fields of aerospace, spaceflight, environment engineering, automobile industry, transportation and construction.

Description

Improve the method for polyimide fiber intensity, modulus, heat endurance and WATER RESISTANCE
Technical field
The invention belongs to high-performance fiber technical field, particularly relate to a kind of method improving polyimide fiber intensity, modulus, heat endurance and water repelling property.
Background technology
Polyimide fiber is one of important kind of high technical fibre, with the dielectric properties of its excellence, radiation resistance and higher strength and modulus, be expected to be widely used in fields such as modern Aviation, military affairs, navigation, environmental project, auto industry, microelectronics.The development of science and technology is had higher requirement to material property, the mechanical property of existing business-like polyimide fiber, heat endurance need to improve (Zheng Weifeng further, Zhou Laishui, Tan Changbai etc. high-performance fiber and developer resin present situation [J]. Xi'an University's journal: natural science edition, 2013,16 (1): 27-31.).And the WATER RESISTANCE of common polyimides is generally poor, the demand (bear is built, and the synthesis and characteries of siliceous alicyclic dianhydride and solubility, agent of low hygroscopicity polyimides studies [D] University Of Nanchang, 2011.) of microelectronic industry cannot be met
How to improve the mechanical property of polyimide fiber, heat endurance, reduce hygroscopicity with improve water repelling property etc. be current problem demanding prompt solution (Zhu Xuan, Qian Mingqiu, Yu Xinhai etc. the Progress in research and development of polyimides and fiber thereof ( ) [J]. synthetic technology and application, 2013,28 (2): 24-29; Zhang Chunling, Qiu Xuepeng, Xue Yanhu etc. draft ratio is on the impact [J] of biphenyl type polyimide fiber pattern orientation and performance. institution of higher education's chemistry report, 2011.32 (4): 952-955.).The method that current improvement improves polyimide fiber performance introduces novel diamines or dianhydride monomer usually in the synthesis of its front aggressiveness polyamic acid, improve raising polyimide fiber performance by changing polyimide structures, or improve polyimide fiber performance by the improvement of polyimides synthesis technique, spining technology.But diamines, dianhydride monomer complicated process of preparation, cost are high, and it is not obvious to improve producing effects of imide fiber performance by means of only the improvement of synthesis technique, spining technology.
The development of modern science and technology proposes requirements at the higher level to the kind of material and performance, and traditional homogenous material can not satisfy the demands.Therefore, use MOLECULE DESIGN and molecular engineering thought to carry out the hydridization of several functions material, with the performance complement realized between material with optimize the direction having become modern material research.Organic/inorganic hybridization material is a kind of new material that development in recent years is got up, organic/inorganic hybridization material is different from traditional composite, its organic phase and inorganic phase site size are all in nanometer range, that have or even molecular water sane level, improved by the inorganic component adulterating a small amount of or improve the performance of macromolecular material.Organic/inorganic hybridization material overcomes the defect in homogenous material and conventional composite materials performance, it have concurrently the advantage of organic material and inorganic material advantage.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method improving polyimide fiber intensity, modulus, heat endurance and water repelling property, the method technique is simple, and cost is low, successful, be applicable to various diamines, dianhydride monomer prepares polyimide fiber, have a extensive future.
The invention provides a kind of method improving polyimide fiber intensity, modulus, heat endurance and water repelling property, in polyimide fiber, add the nano silicon of 5% ~ 10% mass fraction, improve the intensity of polyimide fiber, modulus, heat endurance and water repelling property by the hydridization of silica and polyimides and corresponding technology of preparing thereof.
The method of raising polyimide fiber intensity provided by the invention, modulus, heat endurance and water repelling property, comprises the following steps:
(1) surface modification treatment of nano silicon: nano silicon is joined and is dissolved with in the ethanolic solution of coupling agent, regulate mixed liquor pH value to 3 ~ 5, stir 1 ~ 1.5 hour, ultrasonic disperse 30 ~ 50 minutes, stir centrifugation after 30 ~ 50 minutes again, after absolute ethanol washing, suction filtration 3 ~ 4 times, put into baking oven dry, the grinding of the powder of oven dry is obtained the nano silicon of surface modification
(2) preparation of polyamic acid/SiO 2 hybrid solution: step (1) the gained surface modified nano silicon powder of metering is joined and fills in the reactor of organic solvent, add the coupling agent of metering, carry out mechanical agitation and ultrasonic disperse, after abundant dispersed with stirring, stop ultrasonic disperse, under nitrogen protection, add the diamine monomer of metering, be stirred well to after diamines dissolves completely, metered mol ratio, divide 2 ~ 4 batches and add dianhydride monomer, 0 DEG C ~ 28 DEG C Keep agitation reactions 15 ~ 18 hours, be prepared into polyamic acid/SiO 2 hybrid solution,
(3) described polyamic acid/SiO 2 hybrid solution is carried out vacuum defoamation, then as spinning solution after 200 ~ 300 order silk screen filter;
(4) wet spinning and wet draft process or dry-wet spinning and wet draft process described spinning solution is adopted to be prepared into polyamic acid/SiO 2 hybrid fiber;
(5) described polyamic acid/SiO 2 hybrid fiber is carried out hot-imide and hot gas spring process obtains polyimide/silicon dioxide hybridized fiber.
In said method, described in step (1) and step (2), coupling agent is silane coupler, and the quality of the coupling agent added in step (2) is 1% ~ 4% of nano silicon quality.
In said method, organic solvent described in step (2) is the mixture of one or more in N, N '-dimethyl formamide, N, N '-dimethylacetylamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
In said method, in step (2), diamine monomer and the total mol ratio of dianhydride monomer are 1:1.0 ~ 1.08; In hydridization solution, monomer solid content is 10% ~ 25%.
In said method, wet spinning and wet draft process described in step (4), namely spinning solution is after spinneret orifice ejection, solidifies, wet drawing-off, water washing bath washing, winding receive silk, obtain polyamic acid/SiO 2 hybrid fiber through coagulating bath; Described dry-wet spinning and wet draft process, namely spinning solution sprays from spinneret orifice, after 10mm ~ 60mm air layer, then solidify through coagulating bath, wet drawing-off, water washing bath washing, winding receive silk, obtains polyamic acid/SiO 2 hybrid fiber.
In said method, described in step (4), wet drawing-off drafting multiple is 1 ~ 5 times, and spinning speed is 5 ~ 20 ms/min.
In said method, coagulating bath described in step (4) is dimethyl sulfoxide (DMSO), N, N '-dimethyl formamide, N, the mixed solution of N '-organic solvent such as dimethylacetylamide, METHYLPYRROLIDONE and water, the volume ratio of organic solvent and water is: 1:9 ~ 3:7, and coagulation bath temperature is 2 DEG C ~ 28 DEG C.
In said method; described in step (5), hot-imide is treated under vacuum or nitrogen protection; staged intensification and heat preservation hot process are carried out to polyamic acid/SiO 2 hybrid fiber; described staged heats up and heat preservation hot is treated to; after being warming up to 120 DEG C ~ 130 DEG C by 1 DEG C ~ 5 DEG C/min heating rates, be incubated 30 ~ 60 minutes, then heat up by identical heating rate; often be incubated 30 ~ 60 minutes, until 300 DEG C ~ 550 DEG C after intensification 50 DEG C ~ 60 DEG C.
In said method, the drawing temperature of hot gas spring process described in step (5) is 350 DEG C ~ 550 DEG C, hot gas spring multiple 1 ~ 3.5 times.
The present invention has following novelty and beneficial effect:
1, the invention provides a kind of method improving polyimide fiber intensity, modulus, heat endurance and water repelling property, have no same or similar report so far.
2, the present invention adopts the spinning of inorganic nano silica and polyimide hybrid method and uniqueness and wet drawing-off, staged to heat up and the technology such as heat preservation hot process, hot gas spring, the performances such as the mechanics of polyimide fiber, heat endurance, water resistant are not only made to be improved significantly, and technique is simple, cost is low, is applicable to various diamines, dianhydride monomer prepares polyimide fiber.
3, polyimide/silicon dioxide hybridized fiber provided by the invention overcomes the defect in single material fibre and conventional composite materials fibre property, have the advantage of organic material and inorganic material concurrently, the fields such as Aero-Space, environmental project, auto industry, transportation building can be widely used in, have a extensive future.
Accompanying drawing explanation
The thermogravimetric analysis figure of the polyimide fiber that Fig. 1 provides for the embodiment of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.These embodiments only limit the scope of the invention for illustration of the present invention.Therefore, after the content of having read the present invention's instruction, those skilled in the art can carry out various amendment or equivalent replacement to the present invention, but these equivalent form of values fall within right of the present invention equally.
Embodiment 1
By 20g Nano-meter SiO_2 2join and be dissolved with in the 200mL ethanolic solution of 20mL silane resin acceptor kh-550, regulate pH of mixed to 3, stir 1 hour, ultrasonic disperse 30 minutes, stir centrifugation after 30 minutes again, after absolute ethanol washing, suction filtration 3 times, put into vacuum drying oven dry, the grinding of the powder of oven dry is obtained the nano silicon of surface modification.
Take the above-mentioned SiO through surface modification of 9.56g 2join and fill N, in the four-hole boiling flask of N '-dimethylacetylamide, add 0.096g coupling agent KH-550, carry out mechanical agitation and ultrasonic disperse, work as SiO 2after abundant dispersion; stop ultrasonic disperse, pass into nitrogen, add 102.163g 4; 4'-diaminodiphenyl ether; be stirred well to diamines to dissolve completely, under nitrogen protection and stirring, divide 3 batches to add 110.72 g pyromellitic acid anhydrides by the mol ratio of diamines and dianhydride 1:1; control N; N '-dimethylacetylamide total amount is 669mL, and 0 DEG C ~ 5 DEG C stirring reactions 18 hours, obtain polyamic acid/SiO 2 hybrid solution that monomer solid content is 25%.
After above-mentioned polyamic acid/SiO 2 hybrid solution for vacuum deaeration, 300 order silk screen filter, wet spinning and wet draft process is adopted to carry out spinning, spinning solution enters coagulating bath after being the spinneret orifice ejection of 0.2mm from aperture, solidify through coagulating bath, wet drawing-off, water washing bath washing, winding receive silk, obtain polyamic acid/SiO 2 hybrid fiber.Described wet drafting multiple 1 times, spinning speed is 5 ms/min, and coagulation bath composition is N, N '-dimethylacetylamide and water, volume ratio 1:9, and coagulation bath temperature is 2 DEG C ~ 4 DEG C.
Gained polyamic acid/SiO 2 hybrid fiber is sent in heat-treatment furnace, under vacuum, after being warming up to 120 DEG C by 1 DEG C/min of heating rate, be incubated 60 minutes, then heat up by identical heating rate, be often incubated 60 minutes, until 360 DEG C after intensification 60 DEG C.By the drawing-off 1 times 400 DEG C time of the fiber after hot-imide PROCESS FOR TREATMENT, obtain SiO 2mass fraction is the polyimide/silicon dioxide hybridized fiber of 5%.
Test gained polyimide/silicon dioxide hybridized fiber, its TENSILE STRENGTH is 0.59GPa, and modulus is 7.97GPa, and water absorption rate is 1.31%.
Carry out thermogravimetric analysis to gained polyimide/silicon dioxide hybridized fiber, result is see Fig. 1, and as shown in Figure 1, temperature when embodiment 1 gained polyamic acid/SiO 2 hybrid fiber quality loses 5% is 549.5 DEG C.
Embodiment 2
The SiO through surface modification added in hydridization solution preparation process 2for 19.12g, KH-550 are 0.1912 g, all the other, with embodiment 1, obtain SiO 2mass fraction is the polyimide/silicon dioxide hybridized fiber of 10%.
Test gained hybridized fiber, its TENSILE STRENGTH is 0.65GPa, and modulus is 8.12 GPa, and water absorption rate is 0.97%.
Comparative example l
Nano-meter SiO_2 is not added in hydridization solution preparation process 2and coupling agent, all the other are with embodiment 1.Test without hybrid polyimide fiber obtained, its fracture strength is 0.37 GPa, and modulus is 4.07 GPa, and water absorption rate is 3.74%.
Carry out thermogravimetric analysis to the polyimide fiber of the non-hydridization of gained, result is see Fig. 1, and as shown in Figure 1, temperature when comparative example 1 gained polyamic acid fiber quality loses 5% is 507.3 DEG C.
From comparative example l, by the method for the hydridization of nano silicon and polyimides, the intensity of polyimide/silicon dioxide hybridized fiber, modulus and heat endurance are greatly improved than the polyimide fiber of non-hydridization, water absorption rate then obviously declines, and shows that the water repelling property of polyimide fiber is improved significantly.
Embodiment 3
By embodiment 1 gained polyamic acid/SiO 2 hybrid solution, after vacuum defoamation, 200 order silk screen filter, wet spinning and wet draft process is adopted to carry out spinning, spinneret orifice diameter is 0.8mm, wet drafting multiple 3 times, and spinning speed is 15 ms/min, coagulation bath composition is N, N '-dimethylacetylamide and water, volume ratio 3:7, coagulation bath temperature is 10 DEG C ~ 12 DEG C.
Gained polyamic acid/SiO 2 hybrid fiber is carried out staged intensification, heat preservation hot process under vacuum, after being warming up to 130 DEG C by 3 DEG C/min of heating rates, be incubated 30 minutes, then heat up by identical heating rate, often be incubated 30 minutes after intensification 50 DEG C, until 380 DEG C, by the drawing-off 3 times 500 DEG C time of the fiber after hot-imide PROCESS FOR TREATMENT, obtain SiO 2mass fraction is the polyimide/silicon dioxide hybridized fiber of 5%.Test gained hybridized fiber, its fracture strength is 0.78GPa, and modulus is 13.18 GPa, and water absorption rate is 1.28%.
Comparative example 2
Nano-meter SiO_2 is not added in hydridization solution preparation process 2and coupling agent, all the other are with embodiment 3.Test without hybrid polyimide fiber obtained, its fracture strength is 0.49 GPa, and modulus is 6.84 GPa, and water absorption rate is 3.55%.
From comparative example 2, adulterate inorganic nano silica in polyimide fiber, and improve the intensity of fiber, modulus and heat endurance, and reduce water absorption rate, namely water repelling property is improved significantly.
Embodiment 4
By 25g Nano-meter SiO_2 2join in the 200mL ethanolic solution being dissolved with 25mL silane coupler KH-590, regulate pH of mixed to 4, stir 1.5 hours, ultrasonic disperse 50 minutes, stir centrifugation after 50 minutes, suction filtration again, after absolute ethanol washing, suction filtration 4 times, put into vacuum drying oven dry, the grinding of the powder of oven dry is obtained the nano silicon of surface modification.
Respectively by the above-mentioned SiO through surface modification 27.883g and 0.315 g coupling agent KH-590 joins N, in N'-dimethyl formamide, carries out mechanical agitation and ultrasonic disperse, works as SiO 2after abundant dispersion, stop ultrasonic disperse, pass into nitrogen, by 4, 4 '-diaminodiphenyl ether: 3, 3', 4, 4'-bibenzene tetracarboxylic dianhydride: the mol ratio of pyromellitic acid anhydride=1:0.5:0.58, add 4, 4 '-diaminodiphenyl ether (0.25mol), after diamines dissolves completely, divide 3 batches and add 3 respectively, 3', 4, 4'-bibenzene tetracarboxylic dianhydride (0.125mol) and pyromellitic acid anhydride (0.145mol), control N, N '-dimethyl formamide total amount, monomer solid content is made to be 15%, 10 ~ 15 DEG C of stirring reactions 15 hours, obtain polyamic acid/SiO 2 hybrid solution.
After above-mentioned polyamic acid/SiO 2 hybrid solution for vacuum deaeration, 300 order silk screen filter, adopt dry-wet spinning and wet draft process, namely spinning solution is the spinneret orifice ejection of 0.8mm from aperture, after 10mm air layer, enter coagulating bath, solidify through coagulating bath, wet drawing-off, water washing bath washing, winding receive silk, obtain polyamic acid/SiO 2 hybrid fiber.Described wet drafting multiple 2 times, spinning speed is 20 ms/min, and coagulation bath composition is N, N '-dimethyl formamide and water, volume ratio 2.5:7.5, and coagulation bath temperature is 19 DEG C ~ 20 DEG C.
By described polyamic acid/SiO 2 hybrid fiber under vacuum, carry out staged intensification, heat preservation hot process, after being warming up to 120 DEG C by 5 DEG C/min of heating rates, be incubated 50 minutes, then heat up by identical heating rate, be often incubated 50 minutes, until 300 DEG C after intensification 60 DEG C, by the drawing-off 3.5 times 350 DEG C time of the fiber after hot-imide PROCESS FOR TREATMENT, obtain SiO 2mass fraction is 7.5% polyimide/silicon dioxide hybridized fiber.Test gained hybridized fiber, its fracture strength is 1.27GPa, and modulus is 25.57 GPa.
Embodiment 5
By 25g Nano-meter SiO_2 2join in the 180mL ethanolic solution being dissolved with 25mL silane coupler Si-69, regulate pH of mixed to 5, stir 1.5 hours, ultrasonic disperse 40 minutes, stir centrifugation after 40 minutes again, after absolute ethanol washing, suction filtration 3 times, put into vacuum drying oven dry, the grinding of the powder of oven dry is obtained the nano silicon of surface modification.
By the above-mentioned SiO through surface modification 214.274g and 0.471g Si-69 joins in METHYLPYRROLIDONE, carries out mechanical agitation and ultrasonic disperse, works as SiO 2after abundant dispersion, stop ultrasonic disperse, pass into nitrogen, by 4, 4 '-diaminodiphenyl ether: p-phenylenediamine (PPD): 3, 3', 4, the mol ratio of 4'-bibenzene tetracarboxylic dianhydride=1:3.5:4.53, first by 4, 4 '-diaminodiphenyl ether (0.1mol) and p-phenylenediamine (PPD) (0.35mol) add, be stirred well to diamines to dissolve completely, under nitrogen protection and stirring, divide 4 batches by pyromellitic acid anhydride (0.453mol) again to add, and make monomer solid content be 10%, 23 DEG C ~ 28 DEG C stirring reactions 17 hours, obtain polyamic acid/SiO 2 hybrid solution.
After above-mentioned polyamic acid/SiO 2 hybrid solution for vacuum deaeration, 200 order silk screen filter, adopt dry-wet spinning and wet draft process, namely spinning solution is the spinneret orifice ejection of 0.8mm from aperture, after 60mm air layer, enter coagulating bath, solidify through coagulating bath, wet drawing-off, water washing bath washing, winding receive silk, obtain polyamic acid/SiO 2 hybrid fiber.Described wet drafting multiple 5 times, spinning speed is 15 ms/min, and coagulation bath composition is METHYLPYRROLIDONE and water, volume ratio 2:8, and coagulation bath temperature is 25 DEG C ~ 28 DEG C.
By described polyamic acid/SiO 2 hybrid fiber in nitrogen atmosphere, carry out staged and heat up and heat preservation hot process, after being warming up to 130 DEG C by 3 DEG C/min of heating rates, be incubated 60 minutes, then heat up by identical heating rate, be often incubated 60 minutes, until 550 DEG C after intensification 60 DEG C.By the drawing-off 2 times 550 DEG C time of the fiber after hot-imide PROCESS FOR TREATMENT, obtain SiO 2mass fraction is the polyimide/silicon dioxide hybridized fiber of 8.2%.
Its fracture strength of gained hybridized fiber is 2.45GPa, and modulus is 47.27 GPa, and water absorption rate is 1.02%.
Embodiment 6
Silane coupler used is A-171, and all the other are with embodiment 5.
Its fracture strength of gained hybridized fiber is 2.41GPa, and modulus is 49.31 GPa, and water absorption rate is 1.12%.
Comparative example 3
Nano-meter SiO_2 is not added in hydridization solution preparation process 2and coupling agent, all the other are with embodiment 5.Test obtained non-hybrid polyimide fiber, its fracture strength is 1.13 GPa, and modulus is 24.15 GPa, and water absorption rate is 3.02%.
From comparative example 3, by the method for the hydridization of nano silicon and polyimides, the intensity of polyimide/silicon dioxide hybridized fiber, modulus and heat endurance are greatly improved than the polyimide fiber of non-hydridization, water absorption rate then obviously declines, and shows that the water repelling property of polyimide fiber is improved significantly.
Embodiment 7
By the SiO through surface modification prepared by 8.492 g embodiments 5 2join in dimethyl sulfoxide (DMSO) with 0.212gSi-69, carry out mechanical agitation and ultrasonic disperse, work as SiO 2after abundant dispersion, stop ultrasonic disperse, pass into nitrogen, by 4, 4'-diaminodiphenyl ether: 3, 3'-dimethylbenzidine: pyromellitic acid anhydride: 3, 3'4, the mol ratio of 4'-benzophenone tetracarboxylic dianhydride=1:0.25:1:0.25, add 4, 4'-diaminodiphenyl ether (0.25mol) and 3, 3'-dimethylbenzidine (0.0625mol), be stirred well to diamines to dissolve completely, under nitrogen protection and stirring, again respectively by pyromellitic acid anhydride (0.25mol) and 3, 3'4, 4'-benzophenone tetracarboxylic dianhydride (0.0625mol) is divided 2 batches and is added, and make monomer solid content be 12%, 10 ~ 15 DEG C of stirring reactions 18 hours, obtain polyamic acid/SiO 2 hybrid solution.
After above-mentioned polyamic acid/SiO 2 hybrid solution for vacuum deaeration, 300 order silk screen filter, adopt dry-wet spinning and wet draft process, namely spinning solution is the spinneret orifice ejection of 0.6mm from aperture, after 30mm air layer, enter coagulating bath, solidify through coagulating bath, wet drawing-off, water washing bath washing, winding receive silk, obtain polyamic acid/SiO 2 hybrid fiber.Described wet drafting multiple 2 times, spinning speed is 12 ms/min, and coagulation bath composition is dimethyl sulfoxide (DMSO) and water, volume ratio 2.5:7.5, and coagulation bath temperature is 15 DEG C ~ 17 DEG C.
By gained polyamic acid/SiO 2 hybrid fiber under vacuum, carry out staged to heat up and heat preservation hot process, after being warming up to 120 DEG C by 3 DEG C/min of heating rates, be incubated 30 minutes, then heat up by identical heating rate, be often incubated 30 minutes, until 370 DEG C after intensification 50 DEG C.By the drawing-off 2.5 times 500 DEG C time of the fiber after hot-imide PROCESS FOR TREATMENT, obtain SiO 2mass fraction is the polyimide/silicon dioxide hybridized fiber of 6.7%.
Gained SiO 2content is 6.7% its fracture strength of polyimide/silicon dioxide hybridized fiber is 2.07GPa, and modulus is 35.85 GPa.
Embodiment 8
By 20g Nano-meter SiO_2 2join and be dissolved with in the 170mL ethanolic solution of 16mL silane coupling A-151, regulate pH of mixed to 5, stir 1.2 hours, ultrasonic disperse 40 minutes, stir centrifugation after 40 minutes again, after absolute ethanol washing, suction filtration 2 times, put into vacuum drying oven dry, the grinding of the powder of oven dry is obtained the nano silicon of surface modification.
By above-mentioned for the 10.515g SiO through surface modification 2join with 0.263g A-151 the N that volume ratio is 1:1, in the mixed solvent of N '-dimethyl formamide and N, N '-dimethylacetylamide, carry out mechanical agitation and ultrasonic disperse, work as SiO 2after abundant dispersion, stop ultrasonic disperse, pass into nitrogen; by 4; 4 '-diaminodiphenyl ether: the mol ratio of pyromellitic acid anhydride=1:1.06, first adds 4,4 '-diaminodiphenyl ether (0.5mol); be stirred to diamines to dissolve completely; under nitrogen protection and stirring, then pyromellitic acid anhydride (0.53mol) points 2 batches is added, make monomer solid content be 15%; 12 DEG C ~ 18 DEG C stirring reactions 17 hours, obtain polyamic acid/SiO 2 hybrid solution.
After polyamic acid/SiO 2 hybrid solution for vacuum deaeration, 200 order silk screen filter, adopt dry-wet spinning and wet draft process, namely spinning solution is the spinneret orifice ejection of 0.6mm from aperture, after 20mm air layer, enter coagulating bath, solidify through coagulating bath, wet drawing-off, water washing bath washing, winding receive silk, obtain polyamic acid/SiO 2 hybrid fiber.Described wet drafting multiple 2.5 times, spinning speed is 10 ms/min, and coagulation bath composition is N, N '-dimethyl formamide, N, N '-dimethylacetylamide and water, volume ratio 1:1:8, and coagulation bath temperature is 14 DEG C ~ 15 DEG C.
By described polyamic acid/SiO 2 hybrid fiber in nitrogen atmosphere, carry out staged and heat up and heat preservation hot process, after being warming up to 120 DEG C by 5 DEG C/min of heating rates, be incubated 40 minutes, then heat up by identical heating rate, be often incubated 40 minutes, until 420 DEG C after intensification 50 DEG C.By the drawing-off 2 times 400 DEG C time of the fiber after hot-imide PROCESS FOR TREATMENT, obtain SiO 2mass fraction is the polyimide/silicon dioxide hybridized fiber of 5.5%.
Test gained polyimide/silicon dioxide hybridized fiber, its TENSILE STRENGTH is 0.62GPa, and modulus is 13.73GPa.

Claims (10)

1. one kind is improved the method for polyimide fiber intensity, modulus, heat endurance and WATER RESISTANCE, it is characterized in that: add nano silicon, by the hydridization of nano silicon and polyimides, improve the intensity of polyimide fiber, modulus, heat endurance and water repelling property.
2. the method for raising polyimide fiber intensity according to claim 1, modulus, heat endurance and WATER RESISTANCE, is characterized in that: the nano silicon added shared mass fraction in polyimide fiber is 5% ~ 10%.
3. the method for raising polyimide fiber intensity according to claim 1, modulus, heat endurance and WATER RESISTANCE, is characterized in that: comprise the following steps:
(1) surface modification treatment of nano silicon: nano silicon is joined and is dissolved with in the ethanolic solution of coupling agent, regulate mixed liquor pH value to 3 ~ 5, stir 1 ~ 1.5 hour, ultrasonic disperse 30 ~ 50 minutes, stir centrifugation after 30 ~ 50 minutes again, after absolute ethanol washing, suction filtration 3 ~ 4 times, put into baking oven dry, the grinding of the powder of oven dry is obtained the nano silicon of surface modification;
(2) preparation of polyamic acid/SiO 2 hybrid solution: step (1) the gained surface modified nano silicon powder of metering is joined and fills in the reactor of organic solvent, add the coupling agent of metering, carry out mechanical agitation and ultrasonic disperse, after abundant dispersed with stirring, stop ultrasonic disperse, under nitrogen protection, add the diamine monomer of metering, be stirred well to after diamines dissolves completely, metered mol ratio, divide 2 ~ 4 batches and add dianhydride monomer, 0 DEG C ~ 28 DEG C Keep agitation reactions 15 ~ 18 hours, be prepared into polyamic acid/SiO 2 hybrid solution,
(3) described polyamic acid/SiO 2 hybrid solution is carried out vacuum defoamation, then as spinning solution after 200 ~ 300 order silk screen filter;
(4) wet spinning and wet draft process or dry-wet spinning and wet draft process described spinning solution is adopted to be prepared into polyamic acid/SiO 2 hybrid fiber;
(5) described polyamic acid/SiO 2 hybrid fiber is carried out hot-imide and hot gas spring process obtains polyimide/silicon dioxide hybridized fiber.
4. the method for raising polyimide fiber intensity according to claim 3, modulus, heat endurance and WATER RESISTANCE, it is characterized in that: described in step (1) and step (2), coupling agent is silane coupler, and the quality of the coupling agent added in step (2) is 1% ~ 4% of nano silicon quality.
5. the method for raising polyimide fiber intensity according to claim 3, modulus, heat endurance and WATER RESISTANCE, it is characterized in that: described in step (2), organic solvent is N, the mixture of one or more in N '-dimethyl formamide, N, N '-dimethylacetylamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
6. the method for raising polyimide fiber intensity according to claim 3, modulus, heat endurance and WATER RESISTANCE, is characterized in that: in step (2), diamine monomer and the total mol ratio of dianhydride monomer are 1:1.0 ~ 1.08; In hydridization solution, monomer solid content is 10% ~ 25%.
7. the method for raising polyimide fiber intensity according to claim 3, modulus, heat endurance and WATER RESISTANCE, it is characterized in that: wet spinning and wet draft process described in step (4), namely spinning solution is after spinneret orifice ejection, solidify through coagulating bath, wet drawing-off, water washing bath washing, winding receive silk, obtain polyamic acid/SiO 2 hybrid fiber; Described dry-wet spinning and wet draft process, namely spinning solution sprays from spinneret orifice, after 10mm ~ 60mm air layer, then solidify through coagulating bath, wet drawing-off, water washing bath washing, winding receive silk, obtains polyamic acid/SiO 2 hybrid fiber; Wet drafting multiple is 1 ~ 5 times, and spinning speed is 5 ~ 20 ms/min.
8. the method for raising polyimide fiber intensity according to claim 7, modulus, heat endurance and water repelling property, it is characterized in that: described coagulating bath is dimethyl sulfoxide (DMSO), N, N '-dimethyl formamide, N, the mixed solution of N '-organic solvent such as dimethylacetylamide, METHYLPYRROLIDONE and water, the volume ratio of organic solvent and water is: 1:9 ~ 3:7, and coagulation bath temperature is 2 DEG C ~ 28 DEG C.
9. the method for raising polyimide fiber intensity according to claim 3, modulus, heat endurance and water repelling property, it is characterized in that: described in step (5), hot-imide is treated under vacuum or nitrogen protection, staged intensification and heat preservation hot process are carried out to polyamic acid/SiO 2 hybrid fiber; Described staged heats up and heat preservation hot is treated to, after being warming up to 120 DEG C ~ 130 DEG C by 1 DEG C/min ~ 5 DEG C/min heating rates, be incubated 30 ~ 60 minutes, then heat up by identical heating rate, often be incubated 30 ~ 60 minutes, until 300 DEG C ~ 550 DEG C after intensification 50 DEG C ~ 60 DEG C.
10. a kind of method improving polyimide fiber intensity, modulus, heat endurance and water repelling property according to claim 1 ~ 9 any one, it is characterized in that: the drawing temperature of hot gas spring process described in step (5) is 350 DEG C ~ 550 DEG C, and hot gas spring multiple is 1 ~ 3.5 times.
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