CN104499085B - Improve polyimide fiber intensity, modulus, heat stability and the method for water-resistance - Google Patents

Improve polyimide fiber intensity, modulus, heat stability and the method for water-resistance Download PDF

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CN104499085B
CN104499085B CN201410664198.3A CN201410664198A CN104499085B CN 104499085 B CN104499085 B CN 104499085B CN 201410664198 A CN201410664198 A CN 201410664198A CN 104499085 B CN104499085 B CN 104499085B
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sio
modulus
polyimide fiber
water
fiber
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CN104499085A (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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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention provides a kind of method improving polyimide fiber intensity, modulus, heat stability and water-resistance, the nano silicon of surface-modified process is added in polyimide fiber, by silicon dioxide and the hydridization of polyimides and the Technology such as corresponding spinning and wet drawing-off, hot-imide and hot gas spring process thereof, it is effectively increased the intensity of polyimide fiber, modulus, heat stability and water repelling property.The method of the present invention is simple to operate, low cost, effect is obvious, be applicable to various diamidogen, dianhydride monomer prepares polyimide fiber, overcome the defect in single material fibre and conventional composite materials fibre property, the advantage having organic material and inorganic material concurrently, can be widely applied to the fields such as Aero-Space, environmental project, auto industry, transportation building.

Description

Improve polyimide fiber intensity, modulus, heat stability and the method for water-resistance
Technical field
The invention belongs to high-performance fiber technical field, particularly relate to a kind of raising polyimide fiber intensity, modulus, heat Stability and the method for water repelling property.
Background technology
Polyimide fiber is one of important kind of high technical fibre, with dielectric properties, the radiation resistance of its excellence And higher intensity and modulus, it is expected in fields such as modern Aviation, military affairs, navigation, environmental project, auto industry, microelectronics It is widely used.Material property is had higher requirement by the development of science and technology, existing business-like polyimides The mechanical property of fiber, heat stability need to be improved further (Zheng Weifeng, Zhou Laishui, Tan Changbai etc. high-performance fiber and resin Current situation [J]. Xi'an University's journal: natural science edition, 2013,16 (1): 27-31.).And common polyimides is anti- Aqueous is the most poor, and (Bears is built, siliceous alicyclic dianhydride and solubility, low suction cannot to meet the demand of microelectronic industry The synthesis of moist polyimides and performance study [D] University Of Nanchang, 2011.)
How to improve the mechanical property of polyimide fiber, heat stability, reducing hygroscopicity to improve water repelling property etc. is At present 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 to biphenyl type Polyimide fiber pattern orientation and the impact [J] of performance. institution of higher education's chemistry report, 2011.32 (4): 952-955.).At present Improve improve polyimide fiber performance method generally introduce in the synthesis of its front aggressiveness polyamic acid novel diamidogen or Dianhydride monomer, by change polyimide structures improve improve polyimide fiber performance, or by polyimides synthesis technique, The improvement of spining technology improves polyimide fiber performance.But diamidogen, dianhydride monomer complicated process of preparation, cost are high, and the most logical Cross synthesis technique, spining technology improvement inconspicuous to improve producing effects of imide fiber performance.
The development of modern science and technology proposes requirements at the higher level to kind and the performance of material, and traditional homogenous material is the most not Demand can be met.Therefore, use MOLECULE DESIGN and molecular engineering thought to carry out the hydridization of several functions material, with realize material it Between performance complement and optimize become modern material research direction.Organic/inorganic hybridization material is development in recent years A kind of new material, organic/inorganic hybridization material is different from traditional composite, its organic facies and inorganic phase Site size is all in nanometer range, and the even molecular water sane level having, the inorganic component a small amount of by doping improves or carry The performance of high macromolecular material.Organic/inorganic hybridization material overcomes the defect in homogenous material and conventional composite materials performance, It has concurrently the advantage of organic material and inorganic material advantage.
Summary of the invention
The technical problem to be solved is to provide a kind of raising polyimide fiber intensity, modulus, heat stability With the method for water repelling property, the method technique is simple, low cost, and effect is obvious, it is adaptable to the preparation of various diamidogen, dianhydride monomer is poly- Imide fiber, has a extensive future.
The invention provides a kind of method improving polyimide fiber intensity, modulus, heat stability and water repelling property, Polyimide fiber adds the nano silicon of 5%～10% mass fraction, by the hydridization of silicon dioxide Yu polyimides And technology of preparing improves the intensity of polyimide fiber, modulus, heat stability and water repelling property accordingly.
What the present invention provided improves polyimide fiber intensity, modulus, heat stability and the method for water repelling property, including with Lower step:
(1) surface modification treatment of nano silicon: nano silicon is joined the ethanol dissolved with coupling agent molten In liquid, regulation mixed liquor pH value, to 3～5, stirs 1～1.5 hour, ultrasonic disperse 30～50 minutes, is stirred for 30～50 minutes Rear centrifugation, puts into after absolute ethanol washing, sucking filtration 3～4 times in baking oven and dries, and is ground by the powder body of drying and obtains surface Modified nano silicon
(2) preparation of polyamic acid/SiO 2 hybrid solution: by step (1) the gained surface-modified nano two of metering Silica powder joins in the reactor filling organic solvent, add metering coupling agent, carry out mechanical agitation with ultrasonic point Dissipate, after being sufficiently stirred for dispersion, stop ultrasonic disperse, under nitrogen protection, add the diamine monomer of metering, be stirred well to diamidogen After being completely dissolved, metered mol ratio, point 2 ~ 4 batches add dianhydride monomer, 0 DEG C ~ 28 DEG C continuously stirred reactions 15 ~ 18 Hour, it is prepared into polyamic acid/SiO 2 hybrid solution；
(3) described polyamic acid/SiO 2 hybrid solution is carried out vacuum defoamation, then through 200 ~ 300 mesh silk screen filter Afterwards as spinning solution；
(4) described spinning solution employing wet spinning is prepared with wet draft process with wet draft process or dry-wet spinning Obtain polyamic acid/SiO 2 hybrid fiber；
(5) described polyamic acid/SiO 2 hybrid fiber is carried out hot-imide and hot gas spring processes and obtains polyamides Imines/SiO 2 hybrid fiber.
In said method, described in step (1) and step (2), coupling agent is silane coupler, the idol added in step (2) Quality is nano silicon quality 1%～the 4% of connection agent.
In said method, described in step (2), organic solvent is N, N-dimethylformamide, N, N-dimethylacetamide The mixture of one or more in amine, METHYLPYRROLIDONE, dimethyl sulfoxide.
In said method, in step (2), diamine monomer and the total mol ratio of dianhydride monomer are 1:1.0～1.08；Hydridization solution Middle monomer solid content is 10% ~ 25%.
In said method, wet spinning described in step (4) sprays from spinneret orifice with wet draft process, i.e. spinning solution After, receive silk through coagulating bath solidification, wet drawing-off, water washing bath washing, winding, obtain polyamic acid/SiO 2 hybrid fiber；Described Dry-wet spinning sprays from spinneret orifice with wet draft process, i.e. spinning solution, after 10mm～60mm air layer, then through solidifying Admittedly bathe solidification, wet drawing-off, water washing bath washing, winding receipts silk, obtain 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, N, N-dimethylformamide, N, N-two The organic solvent such as methylacetamide, METHYLPYRROLIDONE and the mixed solution of water, organic solvent with the volume ratio of water is: 1:9～3:7, coagulation bath temperature is 2 DEG C～28 DEG C.
In said method, hot-imide described in step (5) is processed as under vacuum or nitrogen are protected, to polyamide The staged that carries out acid/SiO 2 hybrid fiber heats up and heat preservation hot processes, and described staged heats up and is processed as with heat preservation hot, presses After 1 DEG C～5 DEG C/min of heating rates are warming up to 120 DEG C～130 DEG C, it is incubated 30～60 minutes, then by identical heating rate Heat up, be often incubated 30～60 minutes after intensification 50 DEG C～60 DEG C, until 300 DEG C～550 DEG C.
In said method, the drawing temperature that hot gas spring described in step (5) processes is 350 DEG C～550 DEG C, hot gas spring multiple 1～3.5 times.
The present invention has following novelty and a beneficial effect:
1, the invention provides a kind of method improving polyimide fiber intensity, modulus, heat stability and water repelling property, Have no same or similar report so far.
2, the present invention use the spinning of inorganic nano silicon dioxide and polyimide hybrid method and uniqueness and wet drawing-off, Staged heats up and the Technology such as heat preservation hot process, hot gas spring, not only make the mechanics of polyimide fiber, heat stability, The performances such as water resistant are improved significantly, and technique is simple, low cost, it is adaptable to it is sub-that various diamidogen, dianhydride monomer prepare polyamides Amine fiber.
3, the polyimide/silicon dioxide hybridized fiber that the present invention provides overcomes single material fibre and conventional composite material Defect in material fibre property, the advantage having organic material and inorganic material concurrently, can be widely applied to Aero-Space, environment work The fields such as journey, auto industry, transportation building, 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, the present invention is expanded on further.These embodiments are merely to illustrate the present invention rather than limit The scope of the present invention processed.Therefore, after having read the content that the present invention lectures, the present invention can be carried out by those skilled in the art Various amendments or equivalent, but within these equivalent form of values fall within scope of the presently claimed invention equally.
Embodiment 1
By 20g Nano-meter SiO_22Joining dissolved with in the 200mL ethanol solution of 20mL silane resin acceptor kh-550, regulation mixes Liquid pH to 3, stirs 1 hour, ultrasonic disperse 30 minutes, is stirred for centrifugation after 30 minutes, through absolute ethanol washing, sucking filtration 3 Put into after secondary in vacuum drying oven and dry, the powder body of drying is ground the nano silicon obtaining surface modification.
Weigh the above-mentioned surface-modified SiO of 9.56g2Join and fill N, in the four-hole boiling flask of N-dimethyl acetylamide, Add 0.096g coupling agent KH-550, carry out mechanical agitation and ultrasonic disperse, work as SiO2After fully dispersed, stop ultrasonic disperse, It is passed through nitrogen, adds 102.163g 4,4'-diaminodiphenyl ether, be stirred well to diamidogen and be completely dissolved, protect at nitrogen and stir Mix under state, divide 3 batches to add 110.72 g pyromellitic acid anhydrides by the mol ratio of diamidogen with dianhydride 1:1, control N, N -dimethyl acetylamide total amount is 669mL, and 0 DEG C～5 DEG C stirring is reacted 18 hours, obtains the polyamide that monomer solid content is 25% Acid/SiO 2 hybrid solution.
After above-mentioned polyamic acid/SiO 2 hybrid solution for vacuum deaeration, 300 mesh silk screen filter, use wet spinning Carrying out spinning with wet draft process, spinning solution enters coagulating bath after the spinneret orifice ejection that aperture is 0.2mm, coagulates through coagulating bath Gu, 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-dimethyl acetylamide 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, by 1 DEG C/min After heating rate is warming up to 120 DEG C, it is incubated 60 minutes, then heats up by identical heating rate, be often incubated 60 after intensification 60 DEG C Minute, until 360 DEG C.By the drawing-off 1 times when 400 DEG C of the fiber after hot-imide PROCESS FOR TREATMENT, obtain SiO2Quality Mark is the polyimide/silicon dioxide hybridized fiber of 5%.
Testing gained polyimide/silicon dioxide hybridized fiber, its hot strength is 0.59GPa, and modulus is 7.97GPa, water absorption rate is 1.31%.
Gained polyimide/silicon dioxide hybridized fiber is carried out thermogravimetric analysis, and result sees Fig. 1, as shown in Figure 1, real Executing temperature when example 1 gained polyamic acid/SiO 2 hybrid fiber quality loses 5% is 549.5 DEG C.
Embodiment 2
The surface-modified SiO added in hydridization solution preparation process2It is 0.1912 g for 19.12g, KH-550, its Remaining with embodiment 1, obtain SiO2Mass fraction is the polyimide/silicon dioxide hybridized fiber of 10%.
Testing gained hybridized fiber, its hot strength is 0.65GPa, and modulus is 8.12 GPa, and water absorption rate is 0.97%。
Comparative example l
Hydridization solution preparation process does not adds Nano-meter SiO_22And coupling agent, remaining is with embodiment 1.To prepared without miscellaneous Changing polyimide fiber to test, its fracture strength is 0.37 GPa, and modulus is 4.07 GPa, and water absorption rate is 3.74%.
The polyimide fiber of hydridization non-to gained carries out thermogravimetric analysis, and result sees Fig. 1, as shown in Figure 1, and comparative example 1 Temperature when gained polyamic acid fiber quality loses 5% is 507.3 DEG C.
From comparative example l, by the method for nano silicon Yu the hydridization of polyimides so that polyimides/bis- The intensity of silicon oxide hybridized fiber, modulus and heat stability are greatly improved than the polyimide fiber of non-hydridization, and inhale Water rate is then decreased obviously, 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 mesh silk screen filter, adopt Carrying out spinning with wet spinning and wet draft process, spinneret orifice diameter is 0.8mm, wet drafting multiple 3 times, and spinning speed is 15 M/min, coagulation bath composition is N, N-dimethyl acetylamide and water, volume ratio 3:7, and coagulation bath temperature is 10 DEG C～12 DEG C.
Gained polyamic acid/SiO 2 hybrid fiber carries out staged intensification under vacuum, heat preservation hot processes, After being warming up to 130 DEG C by 3 DEG C/min of heating rates, it is incubated 30 minutes, then heats up by identical heating rate, often heat up 50 It is incubated 30 minutes after DEG C, until 380 DEG C, by the drawing-off 3 times when 500 DEG C of the fiber after hot-imide PROCESS FOR TREATMENT, To SiO2Mass fraction is the polyimide/silicon dioxide hybridized fiber of 5%.Testing gained hybridized fiber, its fracture is strong Degree is 0.78GPa, and modulus is 13.18 GPa, and water absorption rate is 1.28%.
Comparative example 2
Hydridization solution preparation process does not adds Nano-meter SiO_22And coupling agent, remaining is with embodiment 3.To prepared without miscellaneous Changing polyimide fiber to test, its fracture strength is 0.49 GPa, and modulus is 6.84 GPa, and water absorption rate is 3.55%.
From comparative example 2, in polyimide fiber adulterate inorganic nano silicon dioxide, improve fiber intensity, Modulus and heat stability, and reduce water absorption rate, i.e. water repelling property is improved significantly.
Embodiment 4
By 25g Nano-meter SiO_22Join in the 200mL ethanol solution dissolved with 25mL silane coupler KH-590, regulation mixing Liquid pH to 4, stirs 1.5 hours, ultrasonic disperse 50 minutes, centrifugation, sucking filtration after being stirred for 50 minutes, washes through dehydrated alcohol Wash, put in vacuum drying oven after sucking filtration 4 times and dry, the powder body of drying is ground the nano silicon obtaining surface modification.
Respectively by above-mentioned surface-modified SiO27.883g and 0.315 g coupling agent KH-590 joins N, N'-bis- In methylformamide, carry out mechanical agitation and ultrasonic disperse, work as SiO2After fully dispersed, stop ultrasonic disperse, be passed through nitrogen, press 4,4 '-diaminodiphenyl ether: 3,3', 4,4'-bibenzene tetracarboxylic dianhydride: pyromellitic acid anhydride=1:0.5:0.58 mole joins Ratio, addition 4,4 '-diaminodiphenyl ether (0.25mol), after diamidogen is completely dissolved, point 3 batches are separately added into addition 3,3', 4, 4'-bibenzene tetracarboxylic dianhydride (0.125mol) and pyromellitic acid anhydride (0.145mol), control N, and N '-dimethyl Methanamide is total Amount, making monomer solid content is 15%, 10～15 DEG C of stirring reaction 15 hours, obtains polyamic acid/SiO 2 hybrid solution.
After above-mentioned polyamic acid/SiO 2 hybrid solution for vacuum deaeration, 300 mesh silk screen filter, wet-dry change is used to spin Silk and wet draft process, i.e. spinning solution are the spinneret orifice ejection of 0.8mm from aperture, after 10mm air layer, enter solidification Bath, receives silk through coagulating bath solidification, wet drawing-off, water washing bath washing, winding, obtains 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-dimethylformamide and water, volume ratio 2.5: 7.5, coagulation bath temperature is 19 DEG C～20 DEG C.
By described polyamic acid/SiO 2 hybrid fiber under vacuum, carry out at staged intensification, heat preservation hot Reason, after being warming up to 120 DEG C by 5 DEG C/min of heating rates, is incubated 50 minutes, then heats up by identical heating rate, often heats up It is incubated 50 minutes, until 300 DEG C, by the drawing-off 3.5 when 350 DEG C of the fiber after hot-imide PROCESS FOR TREATMENT after 60 DEG C Times, obtain SiO2Mass fraction is 7.5% polyimide/silicon dioxide hybridized fiber.Testing gained hybridized fiber, it breaks Resistance to spalling is 1.27GPa, and modulus is 25.57 GPa.
Embodiment 5
By 25g Nano-meter SiO_22Join in the 180mL ethanol solution dissolved with 25mL silane coupler Si-69, regulation mixing Liquid pH to 5, stirs 1.5 hours, ultrasonic disperse 40 minutes, is stirred for centrifugation after 40 minutes, through absolute ethanol washing, sucking filtration Put into after 3 times in vacuum drying oven and dry, the powder body of drying is ground the nano silicon obtaining surface modification.
By above-mentioned surface-modified SiO214.274g and 0.471g Si-69 joins METHYLPYRROLIDONE In, carry out mechanical agitation and ultrasonic disperse, work as SiO2After fully dispersed, stop ultrasonic disperse, be passed through nitrogen, by 4,4-diamino Yl diphenyl ether: p-phenylenediamine: 3,3', the mol ratio of 4,4'-bibenzene tetracarboxylic dianhydrides=1:3.5:4.53, first by 4,4 '-diamino Yl diphenyl ether (0.1mol) and p-phenylenediamine (0.35mol) add, and are stirred well to diamidogen and are completely dissolved, and protect at nitrogen and stir Mix under state, then pyromellitic acid anhydride (0.453mol) points 4 batches are added, and to make monomer solid content be 10%, 23 DEG C～28 DEG C stirring reaction 17 hours, obtain polyamic acid/SiO 2 hybrid solution.
After above-mentioned polyamic acid/SiO 2 hybrid solution for vacuum deaeration, 200 mesh silk screen filter, wet-dry change is used to spin Silk and wet draft process, i.e. spinning solution are the spinneret orifice ejection of 0.8mm from aperture, after 60mm air layer, enter solidification Bath, receives silk through coagulating bath solidification, wet drawing-off, water washing bath washing, winding, obtains 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, 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 at heat preservation hot Reason, after being warming up to 130 DEG C by 3 DEG C/min of heating rates, is incubated 60 minutes, then heats up by identical heating rate, often heats up It is incubated 60 minutes after 60 DEG C, until 550 DEG C.By the drawing-off 2 times when 550 DEG C of the fiber after hot-imide PROCESS FOR TREATMENT, Obtain SiO2Mass 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 remaining is 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
Hydridization solution preparation process does not adds Nano-meter SiO_22And coupling agent, remaining is with embodiment 5.To prepared non-hydridization Polyimide fiber is tested, and 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 nano silicon Yu the hydridization of polyimides so that polyimides/bis- The intensity of silicon oxide hybridized fiber, modulus and heat stability are greatly improved than the polyimide fiber of non-hydridization, and inhale Water rate is then decreased obviously, and shows that the water repelling property of polyimide fiber is improved significantly.
Embodiment 7
Surface-modified SiO prepared by 8.492 g embodiments 52Dimethyl sulfoxide is joined with 0.212gSi-69 In, carry out mechanical agitation and ultrasonic disperse, work as SiO2After fully dispersed, stop ultrasonic disperse, be passed through nitrogen, by 4,4'-diamino Yl diphenyl ether: 3,3'-dimethylbenzidine: pyromellitic acid anhydride: 3,3'4,4'-benzophenone tetracarboxylic dianhydride=1:0.25: The mol ratio of 1:0.25, addition 4,4'-diaminodiphenyl ether (0.25mol) and 3,3'-dimethylbenzidine (0.0625mol), it is stirred well to diamidogen and is completely dissolved, under nitrogen protection and stirring, more respectively by Pyromellitic Acid Dianhydride (0.25mol) and 3,3'4,4'-benzophenone tetracarboxylic dianhydride (0.0625mol) point 2 batch adds, and makes monomer solid Content is 12%, 10～15 DEG C of stirring reaction 18 hours, obtains polyamic acid/SiO 2 hybrid solution.
After above-mentioned polyamic acid/SiO 2 hybrid solution for vacuum deaeration, 300 mesh silk screen filter, wet-dry change is used to spin Silk and wet draft process, i.e. spinning solution are the spinneret orifice ejection of 0.6mm from aperture, after 30mm air layer, enter solidification Bath, receives silk through coagulating bath solidification, wet drawing-off, water washing bath washing, winding, obtains 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 and water, volume ratio 2.5:7.5, solidifying Gu 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 at heat preservation hot Reason, after being warming up to 120 DEG C by 3 DEG C/min of heating rates, is incubated 30 minutes, then heats up by identical heating rate, often heats up It is incubated 30 minutes after 50 DEG C, until 370 DEG C.By the drawing-off 2.5 when 500 DEG C of the fiber after hot-imide PROCESS FOR TREATMENT Times, obtain SiO2Mass fraction is the polyimide/silicon dioxide hybridized fiber of 6.7%.
Gained SiO2Content be 6.7% its fracture strength of polyimide/silicon dioxide hybridized fiber be 2.07GPa, modulus is 35.85 GPa。
Embodiment 8
By 20g Nano-meter SiO_22Joining dissolved with in the 170mL ethanol solution of 16mL silane coupling A-151, regulation mixes Liquid pH to 5, stirs 1.2 hours, ultrasonic disperse 40 minutes, is stirred for centrifugation after 40 minutes, through absolute ethanol washing, sucking filtration Put into after 2 times in vacuum drying oven and dry, the powder body of drying is ground the nano silicon obtaining surface modification.
By above-mentioned for 10.515g surface-modified SiO2The N that volume ratio is 1:1, N-two is joined with 0.263g A-151 Methylformamide and N, in the mixed solvent of N-dimethyl acetylamide, carry out mechanical agitation and ultrasonic disperse, work as SiO2Fully divide After Saning, stop ultrasonic disperse, be passed through nitrogen, by 4,4-diaminodiphenyl ether: pyromellitic acid anhydride=1:1.06 mole joins Ratio, first adds 4,4 '-diaminodiphenyl ether (0.5mol), stirs and is completely dissolved to diamidogen, protects and stirring at nitrogen Under, then pyromellitic acid anhydride (0.53mol) point 2 batch is added, making monomer solid content is 15%, and 12 DEG C～18 DEG C stirrings are anti- Answer 17 hours, obtain polyamic acid/SiO 2 hybrid solution.
After polyamic acid/SiO 2 hybrid solution for vacuum deaeration, 200 mesh silk screen filter, use dry-wet spinning with Wet draft process, i.e. spinning solution are the spinneret orifice ejection of 0.6mm from aperture, after 20mm air layer, enter coagulating bath, warp Coagulating bath solidification, wet drawing-off, water washing bath washing, winding receive silk, obtain polyamic acid/SiO 2 hybrid fiber.Described wet drawing-off Multiple 2.5 times, spinning speed is 10 ms/min, and coagulation bath composition is N, N-dimethylformamide, N, N-dimethylacetamide Amine and water, volume ratio 1:1:8, 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 at heat preservation hot Reason, after being warming up to 120 DEG C by 5 DEG C/min of heating rates, is incubated 40 minutes, then heats up by identical heating rate, often heats up It is incubated 40 minutes after 50 DEG C, until 420 DEG C.By the drawing-off 2 times when 400 DEG C of the fiber after hot-imide PROCESS FOR TREATMENT, Obtain SiO2Mass fraction is the polyimide/silicon dioxide hybridized fiber of 5.5%.
Testing gained polyimide/silicon dioxide hybridized fiber, its hot strength is 0.62GPa, and modulus is 13.73GPa。

Claims (5)

1. the method improving polyimide fiber intensity, modulus, heat stability and water-resistance, is characterized in that: add nanometer Silicon dioxide, by the hydridization of nano silicon Yu polyimides, improves the intensity of polyimide fiber, modulus, thermally-stabilised Property and water repelling property；
Comprise the following steps:
(1) surface modification treatment of nano silicon: nano silicon is joined dissolved with in the ethanol solution of coupling agent, Regulation mixed liquor pH value, to 3～5, stirs 1～1.5 hour, ultrasonic disperse 30～50 minutes, centrifugal after being stirred for 30～50 minutes Separate, put into after absolute ethanol washing, sucking filtration 3～4 times in baking oven and dry, the powder body of drying is ground and obtains surface modification Nano silicon；
(2) preparation of polyamic acid/SiO 2 hybrid solution: by step (1) the gained surface-modified nano titanium dioxide of metering Silicon powder joins in the reactor filling organic solvent, adds the coupling agent of metering, carries out mechanical agitation and ultrasonic disperse, fill After dividing dispersed with stirring, stop ultrasonic disperse, under nitrogen protection, add the diamine monomer of metering, be stirred well to diamidogen complete After dissolving, metered mol ratio, point 2～4 batches add dianhydride monomer, little 0 DEG C～28 DEG C continuously stirred reaction 15～18 Time, it is prepared into polyamic acid/SiO 2 hybrid solution；
(3) described polyamic acid/SiO 2 hybrid solution is carried out vacuum defoamation, then make after 200～300 mesh silk screen filter For spinning solution；
(4) described spinning solution employing wet spinning is prepared into poly-with wet draft process or dry-wet spinning with wet draft process Amic acid/SiO 2 hybrid fiber；
(5) described polyamic acid/SiO 2 hybrid fiber is carried out hot-imide and hot gas spring process obtain polyimides/ SiO 2 hybrid fiber.
Raising polyimide fiber intensity the most according to claim 1, modulus, heat stability and the method for water-resistance, its Feature is: the nano silicon of addition shared mass fraction in polyimide fiber is 5%～10%.
Raising polyimide fiber intensity the most according to claim 1, modulus, heat stability and the method for water-resistance, its It is characterised by: described in step (1) and step (2), coupling agent is silane coupler, the quality of the coupling agent added in step (2) For nano silicon quality 1%～4%.
Raising polyimide fiber intensity the most according to claim 1, modulus, heat stability and the method for water-resistance, its Feature is: described in step (2), organic solvent is N, N '-dimethylformamide, N, N '-dimethyl acetylamide, N-methyl-2-pyrrole The mixture of one or more in pyrrolidone, dimethyl sulfoxide.
Raising polyimide fiber intensity the most according to claim 1, modulus, heat stability and the method for water-resistance, its Feature is: in step (2), diamine monomer and the total mol ratio of dianhydride monomer are 1:1.0～1.08；Monomer solid content in hydridization solution It is 10%～25%.
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