CN107151833B - A kind of polyimide fine denier fiber and preparation method thereof - Google Patents
A kind of polyimide fine denier fiber and preparation method thereof Download PDFInfo
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- CN107151833B CN107151833B CN201710513768.2A CN201710513768A CN107151833B CN 107151833 B CN107151833 B CN 107151833B CN 201710513768 A CN201710513768 A CN 201710513768A CN 107151833 B CN107151833 B CN 107151833B
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- 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
- D01D10/06—Washing or drying
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- 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
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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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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Abstract
A kind of polyimide fine denier fiber and preparation method thereof, belongs to fiber preparation field, solves the problems, such as that end breakage rate existing for the preparation method of existing polyimide fine denier fiber is high, yarn unevenness is high, production efficiency is low.A kind of polyimide fine denier fiber of the invention is by dissolving the soluble composition in polyamic acid two-component as-spun fibre using solvent, it is obtained after washed again, drying, hot imidization, draft process processing, its filament number is 0.5~1.1dtex, and tensile strength is greater than 4.0cN/dtex.Spinning technique of the invention is simple and efficient, production cost is low, and spinning process is stablized safety and is easily industrialized and continuous production, and organic solvent used in spinning process is easily recycled, energy conservation and environmental protection, spinning break rate is reduced, improves yarn unevenness, and then improve production efficiency.The polyimide fine denier fiber excellent combination property obtained by above-mentioned preparation process.
Description
Technical field
The invention belongs to technical field of fiber preparation, and in particular to a kind of polyimide fine denier fiber and its preparation side
Method.
Background technique
Polyimide fiber is a kind of high-performance fiber, and fire resistant polyimide fiber therein is to use temperature most at present
One of high organic synthetic fibers can use at 250~350 DEG C, and light resistance, water imbibition, heat resistance etc. compare
Aramid fiber and polyphenylene sulfide fibre are all more superior.High-performance polyimide fiber is the best organic synthesis of current mechanical property
One of fiber is widely used in the fields such as aerospace, environmental protection, fire prevention.And compared with the polyimide fiber of conventional fineness,
Polyimide fine denier fiber is low with more properties, such as bigger serface, high temperature resistant, thermal conductivity, such as in high temperature
Fine filtering field, can effectively improve filtering accuracy；In heat-barrier material field, fine-denier fiber is used to prepare as reinforcement
Heat-insulation composite material, mechanical property and heat-proof quality obtain raising by a relatively large margin.Fine-denier fiber generally refers to fiber number and exists
Fiber between 0.55~1.1dtex has been widely used at present with excellent adsorptivity, flexibility and comfort
The fields such as household takes, industrial production, space material.
The preparation method of presently disclosed polyimides fine-denier number, micro Denier or superfine Denier fibre has dry method, wet spinning
Method.As the Chinese patent of Publication No. CN102978734A discloses a kind of " preparation side of denier/superfine denier polyimide fiber
Method ", in order to obtain fine-denier number or super fine denier polyimide fiber, which introduce the diamines containing lipid structure, realize fiber
High drafting reduce fibre number, but after introducing diamines or other monomers for containing flexible group segment, or it is more or
The heat resistance of polyimide fiber is sacrificed in few meeting, or even influences the chemical resistance of polyimide fiber.Such as Publication No.
The Chinese patent of CN105648567A discloses " a kind of polyimides superfine fibre and preparation method thereof ", passes through pore spinneret
Fibre number is reduced with biggish spray Lapie, but tiny the hole diameter of spinneret easily occurs to glue in as-spun fibre forming process
Even, cause as-spun fibre meticulous, to generate high end breakage rate, high yarn unevenness and poor efficiency under larger draw ratio
Deng, be also required to carry out polymer molecular structure special design to meet larger spray Lapie, have limitation.
Method of electrostatic spinning: as the Chinese patent of Publication No. CN104480641A discloses, " a kind of high-pressure electrostatic needle spinning is poly-
The large-scale continuous weaving system of acid imide nanofiber " spins polyimide nano-fiber using high-pressure electrostatic needle, and system is huge
Big and complicated, fibre diameter is chiefly used in preparing polyimides superfine fibre film (non-woven membrane) between 3~500nm, is difficult
Obtain the polyimide fiber of continuous tow state.
Co-blended spinning method: as the Chinese patent of Publication No. CN103541040 discloses the " preparation of polylactic acid superfine fibre
Method and polylactic acid superfine fibre ", the blend components using polylactic acid and with polylactic acid non-conforming, organic molten after melt spinning
Component is blended in removal in agent, obtains superfine fibre.But it is this by blend and m eltspinning, then component is blended in removal in a solvent
Method can not be suitable for polyimide fiber (the polyimide molecule structure of spinning is suitble to hardly to melt), and at present
Also component is blended using removal after being blended without any related polyimide fiber and obtains super fine denier, micro Denier or fine-denier number fiber
Report.
Summary of the invention
In order to solve end breakage rate existing for the preparation method of existing polyimide fine denier fiber is high, yarn unevenness is high,
The low problem of production efficiency, the present invention provide a kind of high production efficiency, quality stable polyimide fine denier fiber and its system
Preparation Method.
Used technical solution is as follows in order to solve the technical problem by the present invention:
A kind of polyimide fine denier fiber of the invention, it is nascent by dissolving polyamic acid two-component using solvent
It is obtained after soluble composition in fiber, then washed, drying, hot imidization, draft process processing, filament number 0.5
~1.1dtex, tensile strength are greater than 4.0cN/dtex.
The present invention also provides a kind of above-mentioned preparation methods of polyimide fine denier fiber, comprising the following steps:
Step 1: the preparation of polyamic acid spinning solution I
Be (0.9~1.1) using solvent A dissolution diamines, then in dianhydride and diamines molar ratio: 1 ratio is added thereto
The total amount of dianhydride, dianhydride and diamines makes the solid content 15~30% of polyamic acid solution, and 10~50 DEG C of temperature, reaction 8~
20h obtains polyamic acid spinning solution I, and apparent viscosity is 50000~300000cp, after filtering 8~15h of vacuum defoamation；
Step 2: the preparation of the second component spinning solution II
Mixture A is added into solvent B and is configured to the second component spinning solution II, in the second component spinning solution II, mixing
The mass percent of object A is 1~50%, and the solid content of the second component spinning solution II is 30~50%, 8~15h is stirred, through filtering
6~12h deaeration is stood afterwards；
The mixture A is selected from one or both of polyvinyl alcohol, polyvinylpyrrolidone；
Step 3: the preparation of two-component mixing as-spun fibre
Polyamic acid spinning solution I is uniformly mixed with the second component spinning solution II, in the mixed solution, the polyamide
The mass percent of sour spinning solution I is 40~70%, and the mass percent of the second component spinning solution II is 60~30%, benefit
The mixed solution is sprayed with the porous spinneret that aperture is 0.04~0.1mm, obtains two-component mixing as-spun fibre；
Step 4: the removal of the second component
The two-component that step 3 obtains is mixed into as-spun fibre and is staged through dissolving tank 1, dissolving tank 2 and kitchen sink to remove
Second component obtains polyamic acid as-spun fibre；
The mixed solution of deionized water and solvent C, in the mixed solution, deionized water are added in the dissolving tank 1
Mass percent is 60~90%, and the mass percent of solvent C is 40~10%, and the temperature of mixed solution is controlled 20~60
℃；
The mixed solution of deionized water and solvent D, in the mixed solution, deionized water are added in the dissolving tank 2
Mass percent is 60~90%, and the mass percent of solvent C is 40~10%, and the temperature of mixed solution is controlled 20~60
℃；
Deionized water is added in the kitchen sink, temperature is controlled at 20~60 DEG C；
Step 5: the post-processing of polyamic acid as-spun fibre
The polyamic acid as-spun fibre that step 4 obtains successively is obtained after drying, the heat treatment of segmentation warm area, stretch processing
Obtain polyimide fine denier fiber.
As preferred embodiment, the solvent A is identical as solvent B.
As preferred embodiment, in step 1, the solvent A is selected from dimethyl acetamide, dimethylformamide, N, N
One of dimethyl pyrrolidone, dimethyl sulfoxide, tetrahydrofuran are a variety of.
As preferred embodiment, in step 1, the dianhydride be selected from equal benzene dianhydride, biphenyl dianhydride, two ether dianhydride of triphen,
One of diphenyl ether dianhydride, thioether dianhydride, benzophenone dianhydride, Bisphenol A Type Diether Dianhydride are a variety of.
As preferred embodiment, in step 1, the diamines be selected from 4,4 '-diaminodiphenyl ether diamines, p-phenylenediamine,
One of two ether diamine of hexichol, two ether diamine of bisphenol A-type are a variety of.
As preferred embodiment, in step 2, the solvent B is selected from dimethyl acetamide, dimethylformamide, N, N
One of dimethyl pyrrolidone, dimethyl sulfoxide, tetrahydrofuran are a variety of.
As preferred embodiment, in step 4, the solvent C is selected from dimethyl acetamide, dimethylformamide, N, N
One of dimethyl pyrrolidone, dimethyl sulfoxide, tetrahydrofuran are a variety of.
As preferred embodiment, in step 4, the solvent D is selected from dimethyl acetamide, dimethylformamide, N, N
One of dimethyl pyrrolidone, dimethyl sulfoxide, tetrahydrofuran are a variety of.
As preferred embodiment, detailed process is as follows for step 5:
By step 4 obtain polyamic acid as-spun fibre through 50~90 DEG C of dryings, 120~400 DEG C of segmentation warm area heat at
Reason, 400~500 DEG C of stretch processings, draw ratio are 0.5~2 times, obtain polyimide fine denier fiber.
The beneficial effects of the present invention are:
The present invention makes polyamic acid spinning solution and the second component spinning solution under the conditions of same solvent, then using normal
It advises porous spinneret and spins two-component mixing as-spun fibre, then washing methods is dissolved by solvent and removes soluble composition therein,
Part, which is not completely dissolved to remove clean soluble composition and can also aoxidize during rear process high-temperature is heat-treated (hot imidization), to be divided
It solves and removes, do not need big drafting multiple, the polyimide fine denier fiber of excellent combination property can be prepared.
The spinning technique of polyimide fine denier fiber of the invention is simple and efficient, at low cost, and spinning process stablizes safety
And be easily industrialized and continuous production, organic solvent used in spinning process is easily recycled, and reduces production
Cost, energy conservation and environmental protection can reduce spinning break rate, improve yarn unevenness, and then improve production efficiency.Pass through above-mentioned preparation
The polyimide fine denier fibre section that technique obtains is irregular shape, can further increase the specific surface area of fiber, list
Silk size is 0.5~1.1dtex, and tensile strength is greater than 4.0cN/dtex, excellent combination property.
Specific embodiment
A kind of polyimide fine denier fiber of the invention, it is nascent by dissolving polyamic acid two-component using solvent
It is obtained after the process such as the soluble composition in fiber, then washed, drying, hot imidization, drawing-off, polyamides obtained is sub-
Amine fine-denier fiber filament number is 0.5~1.1dtex, and tensile strength is greater than 4.0cN/dtex.
The present invention also provides a kind of above-mentioned preparation methods of polyimide fine denier fiber, and specific preparation process is such as
Under:
Step 1: the preparation of polyamic acid spinning solution I
Solvent A is added in reaction kettle I with agitating device；Agitating device is opened, in nitrogen (N2) protection under be added one
Quantitative diamines, until dissolution is without obvious particle；Then be (0.9~1.1) according to diamines molar ratio by dianhydride: 1 ratio adds
Enter into reaction kettle I, the diamines of addition and the total amount of dianhydride can make polyamic acid solution solid content 15~30%, in temperature
8~20h is reacted under the conditions of being 10~50 DEG C, obtains polyamic acid spinning solution I, and the apparent viscosity of polyamic acid spinning solution I is
50000~300000cp, it is spare after 8~15h of vacuum defoamation after filtering.
Described solvent A is selected from dimethyl acetamide (DMAC), dimethylformamide (DMF), N, N dimethyl pyrrolidones
(NMP), one of dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) or a variety of.
Preferably, described solvent A can be dimethyl acetamide (DMAC) or dimethyl acetamide (DMAC).
Described dianhydride is selected from equal benzene dianhydride (PMDA), biphenyl dianhydride (BPDA), two ether dianhydride of triphen (HQDPA), hexichol
One of ether dianhydride (ODPA), thioether dianhydride (TDPA), benzophenone dianhydride (BTDA), Bisphenol A Type Diether Dianhydride (BPADA)
Or it is a variety of.
Preferably, described dianhydride can be equal benzene dianhydride (PMDA) or biphenyl dianhydride (BPDA).
Described diamines is selected from 4,4 '-diaminodiphenyl ether diamines (ODA), p-phenylenediamine (PPD), two ether diamine of hexichol
(APB), one of two ether diamine of bisphenol A-type (BAPP) or a variety of.
Preferably, described diamines can be 4,4 '-diaminodiphenyl ether diamines (ODA) or p-phenylenediamine (PPD).
Step 2: the preparation of the second component spinning solution II
Reaction kettle II with agitating device is added solvent B, mixture A is slowly added into reaction kettle II, mixture
A reacts with solvent B, is configured to the second component spinning solution II, in the second component spinning solution II, the quality hundred of mixture A
Score is 1~50%, and the solid content of the second component spinning solution II obtained is 30~50%, and 8~15h of stirring is to completely molten
It is spare to stand 6~12h deaeration after filtering for solution.
Described solvent B is selected from dimethyl acetamide (DMAC), dimethylformamide (DMF), N, N dimethyl pyrrolidones
(NMP), one of dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) or a variety of.
Preferably, solvent A is identical as solvent B.
Preferably, described solvent B can be dimethyl acetamide (DMAC) or dimethyl acetamide (DMAC).
Described mixture A is selected from one or both of polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP).
Step 3: the preparation of as-spun fibre
Using metering pump according to ratio accurate measurement polyamic acid spinning solution I and the second component spinning solution II is calculated, then
It is pumped into mixed-hopper respectively, and be sufficiently mixed stirring to guarantee to be uniformly mixed, obtain mixture B, mixing
In object B, the mass percent of polyamic acid spinning solution I is 40~70%, and the mass percent of the second component spinning solution II is 60
~30%, it is sprayed jointly by porous spinneret after evenly mixing, the aperture of spinneret is 0.04~0.1mm, obtains two-component
Mix as-spun fibre.
Step 4: the post-processing (post-processing of removal and polyamic acid as-spun fibre including the second component) of as-spun fibre
Mixing as-spun fibre with two-component prepared by step 3 is staged through dissolving tank 1, dissolving tank 2, kitchen sink.
Wherein, the mixed solution of deionized water and solvent C, in the mixed solution, the quality percentage of deionized water are added in dissolving tank 1
Number is 60~90%, and the mass percent of solvent C is 40~10%, and the temperature of mixed solution is controlled 20~60 in dissolving tank 1
℃；The mixed solution of deionized water and solvent D, in the mixed solution, the mass percent of deionized water are added in dissolving tank 2
It is 60~90%, the mass percent of solvent C is 40~10%, and the temperature of mixed solution is controlled at 20~60 DEG C in dissolving tank 2；
Deionized water is added in kitchen sink, water temperature is controlled at 20~60 DEG C；The two-component of above-mentioned acquisition is mixed as-spun fibre gradually to pass through
Dissolving tank 1, dissolving tank 2 and kitchen sink are crossed to remove the second component, obtains polyamic acid as-spun fibre；Polyamic acid obtained
As-spun fibre through 50~90 DEG C of drying, 120~400 DEG C of segmentation warm area heat treatment, 400~500 DEG C of stretch processing, is drawn again
Stretching multiple is 0.5~2 times, can be obtained polyimide fine denier fiber of the invention.Polyimide fine denier of the invention is fine
Dimension filament number is 0.5~1.1dtex (dividing Tekes), and tensile strength is greater than 4.0cN/dtex, and elongation is 15~25%, whole
The continuous production of polyimide fine denier fiber may be implemented in set preparation process.
Described solvent C is selected from dimethyl acetamide (DMAC), dimethylformamide (DMF), N, N dimethyl pyrrolidones
(NMP), one of dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) or a variety of.
Preferably, described solvent C can be dimethyl acetamide (DMAC) or dimethylformamide (DMF).
Described solvent D is selected from dimethyl acetamide (DMAC), dimethylformamide (DMF), N, N dimethyl pyrrolidones
(NMP), one of dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) or a variety of.
Preferably, described solvent D can be dimethyl acetamide (DMAC) or dimethylformamide (DMF).
Embodiment 1PMDA/ODA polyamic acid solution, with PVA solution co-blended spinning
Step 1: the preparation of polyamic acid spinning solution I
DMAC is added in reaction kettle I with agitating device；Agitating device is opened, in nitrogen (N2) protection under be added one
Quantitative ODA, until dissolution is without obvious particle；Then PMDA is added to and is reacted according to the ratio that ODA molar ratio is 0.95:1
In kettle I, the total amount of the ODA and PMDA of addition can make polyamic acid solution solid content 15%, under the conditions of temperature is 20 DEG C
8h is reacted, polyamic acid spinning solution I is obtained, the apparent viscosity of polyamic acid spinning solution I is 180000cp, after filtering vacuum
It is spare after deaeration 12h.
Step 2: the preparation of the second component spinning solution II
Reaction kettle II with agitating device is added DMAC, polyvinyl alcohol (PVA) is slowly added into reaction kettle II,
Polyvinyl alcohol (PVA) reacts with DMAC, is configured to the second component spinning solution II, in the second component spinning solution II, poly- second
The mass percent of enol (PVA) is 50%, and the solid content of the second component spinning solution II is 40%, and stirring 12h is to completely molten
It is spare to stand 6h deaeration after filtering for solution.
Step 3: the preparation of as-spun fibre
Using metering pump according to ratio accurate measurement polyamic acid spinning solution I and the second component spinning solution II is calculated, then
It is pumped into mixed-hopper respectively, and be sufficiently mixed stirring to guarantee to be uniformly mixed, obtain mixture B, mixing
In object B, the mass percent of polyamic acid spinning solution I is 40%, and the mass percent of the second component spinning solution II is 60%,
It is sprayed jointly after even mixing by porous spinneret, the aperture of spinneret is 0.06mm, obtains two-component mixing as-spun fibre.
Step 4: the post-processing of as-spun fibre
Mixing as-spun fibre with two-component prepared by step 3 is staged through dissolving tank 1, dissolving tank 2, kitchen sink.
Wherein, the mixed solution of deionized water and DMAC, in the mixed solution, the quality percentage of deionized water are added in dissolving tank 1
The mass percent that number is 70%, DMAC is 30%；The mixed solution of deionized water and DMAC is added in dissolving tank 2, it is mixed at this
It closes in solution, the mass percent that the mass percent of deionized water is 70%, DMAC is 30%, in dissolving tank 1 and dissolving tank 2
The temperature of mixing liquid is controlled at 50 DEG C；Deionized water is added in kitchen sink, water temperature is controlled at 30 DEG C；By the double of above-mentioned acquisition
Component mixing as-spun fibre is staged through dissolving tank 1, dissolving tank 2 and kitchen sink to remove the second component, at the beginning of obtaining polyamic acid
Raw fiber；Polyamic acid as-spun fibre obtained again through 90 DEG C of drying, 150 DEG C~350 DEG C of segmentation warm area Continuous Heat at
Reason, 450 DEG C of stretch processing, draw ratio are 1.5 times, can be obtained polyimide fine denier fiber of the invention.The polyamides
Imines fine-denier fiber filament number is 0.9dtex (dividing Tekes), tensile strength 4.2cN/dtex, elongation 20%.
Embodiment 2PMDA, BPDA/ODA polyamic acid solution, with PVP solution blending spinning
Step 1: the preparation of polyamic acid spinning solution I
NMP is added in reaction kettle I with agitating device；Agitating device is opened, in nitrogen (N2) protection under be added it is certain
The ODA of amount, until dissolution is without obvious particle；Then by dianhydride (mixture of PMDA and BPDA, the wherein molar ratio of PMDA and BPDA
Be added in reaction kettle I for 0.7:0.3) according to ratio that ODA molar ratio is 1:1, the ODA and dianhydride of addition (PMDA with
The mixture of BPDA) total amount can make polyamic acid solution solid content 16%, temperature be 10 DEG C under the conditions of react 15h,
Polyamic acid spinning solution I is obtained, the apparent viscosity of polyamic acid spinning solution I is 250000cp, after filtering vacuum defoamation 8h
It is spare afterwards.
Step 2: the preparation of the second component spinning solution II
Reaction kettle II with agitating device is added NMP, polyvinylpyrrolidone (PVP) is slowly added into reaction kettle
In II, polyvinylpyrrolidone (PVP) reacts with NMP, the second component spinning solution II is configured to, in the second component spinning solution
In II, the mass percent of polyvinylpyrrolidone (PVP) is 1%, and the solid content of the second component spinning solution II is 50%, is stirred
8h is mixed to being completely dissolved, it is spare to stand 12h deaeration after filtering.
Step 3: the preparation of as-spun fibre
Using metering pump according to ratio accurate measurement polyamic acid spinning solution I and the second component spinning solution II is calculated, then
It is pumped into mixed-hopper respectively, and be sufficiently mixed stirring to guarantee to be uniformly mixed, obtain mixture B, mixing
In object B, the mass percent of polyamic acid spinning solution I is 40%, and the mass percent of the second component spinning solution II is 60%,
It is sprayed jointly after even mixing by porous spinneret, the aperture of spinneret is 0.04mm, obtains two-component mixing as-spun fibre.
Step 4: the post-processing of as-spun fibre
Mixing as-spun fibre with two-component prepared by step 3 is staged through dissolving tank 1, dissolving tank 2, kitchen sink.
Wherein, the mixed solution of deionized water and NMP, in the mixed solution, the mass percent of deionized water are added in dissolving tank 1
Mass percent for 60%, NMP is 40%；The mixed solution of deionized water and NMP is added in dissolving tank 2, it is molten in the mixing
In liquid, the mass percent that the mass percent of deionized water is 60%, NMP is 40%, is mixed in dissolving tank 1 and dissolving tank 2
The temperature of liquid is controlled at 60 DEG C；Deionized water is added in kitchen sink, water temperature is controlled at 30 DEG C；By the two-component of above-mentioned acquisition
Mixing as-spun fibre is staged through dissolving tank 1, dissolving tank 2 and kitchen sink to remove the second component, obtains the nascent fibre of polyamic acid
Dimension；Polyamic acid as-spun fibre obtained again through 60 DEG C of drying, 120 DEG C~360 DEG C of segmentation warm area continuous heat,
430 DEG C of stretch processing, draw ratio are 0.5 times, can be obtained polyimide fine denier fiber of the invention.The polyimides
Fine-denier fiber filament number is 0.5dtex (dividing Tekes), tensile strength 4.3cN/dtex, elongation 22%.
Embodiment 3PMDA, HQDPA/ODA polyamic acid solution, with PVA/PVP solution blending spinning
Step 1: the preparation of polyamic acid spinning solution I
DMAC is added in reaction kettle I with agitating device；Agitating device is opened, in nitrogen (N2) protection under be added one
Quantitative ODA, until dissolution is without obvious particle；Then by dianhydride, (mixture of PMDA and HQDPA, wherein PMDA and HQDPA rubs
Your ratio is 0.88:0.1) it is added in reaction kettle I according to ratio that ODA molar ratio is 0.98:1, the ODA and dianhydride of addition
The total amount of (mixture of PMDA and HQDPA) can make polyamic acid solution solid content 30%, under the conditions of temperature is 50 DEG C
20h is reacted, polyamic acid spinning solution I is obtained, the apparent viscosity of polyamic acid spinning solution I is 210000cp, after filtering very
It is spare after empty deaeration 15h.
Step 2: the preparation of the second component spinning solution II
DMAC is added in reaction kettle II with agitating device；Mixture A is slowly added into reaction kettle II, mixture A
It reacts with DMAC, is configured to the second component spinning solution II, in the second component spinning solution II, the quality percentage of mixture A
Number is 30%, and the solid content of the second component spinning solution II is 30%, stirs 15h to being completely dissolved, it is de- to stand 9h after filtering
It steeps spare.
Said mixture A is the mixture of polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP), the matter of PVA and PVP
Amount is than being 1:1.
Step 3: the preparation of as-spun fibre
Using metering pump according to ratio accurate measurement polyamic acid spinning solution I and the second component spinning solution II is calculated, then
It is pumped into mixed-hopper respectively, and be sufficiently mixed stirring to guarantee to be uniformly mixed, obtain mixture B, mixing
In object B, the mass percent of polyamic acid spinning solution I is 60%, and the mass percent of the second component spinning solution II is 40%,
It is sprayed jointly after even mixing by porous spinneret, the aperture of spinneret is 0.08mm, obtains two-component mixing as-spun fibre.
Step 4: the post-processing of as-spun fibre
Mixing as-spun fibre with two-component prepared by step 3 is staged through dissolving tank 1, dissolving tank 2, kitchen sink.
Wherein, deionized water and the mixture of DMAC and DMSO, in the mixed solution, the matter of deionized water are added in dissolving tank 1
The mass percent that the mass percent that amount percentage is 70%, DMAC is 20%, DMSO is 20%, and temperature is 40 DEG C；Dissolution
The mixed solution of deionized water and DMAC is added in pond 2, in the mixed solution, the mass percent of deionized water is 60%,
The mass percent of DMAC is 40%, and temperature is 50 DEG C；Deionized water is added in kitchen sink, water temperature is controlled at 30 DEG C；It will be above-mentioned
The two-component mixing as-spun fibre of acquisition is staged through dissolving tank 1, dissolving tank 2 and kitchen sink to remove the second component, is gathered
Amic acid as-spun fibre；The polyamic acid as-spun fibre obtained segmentation warm area through 50 DEG C of drying, 150 DEG C~400 DEG C again
Continuous heat, 410 DEG C of stretch processing, draw ratio are 2 times, can be obtained polyimide fine denier fiber of the invention.
The polyimide fine denier filament fineness is 1.1dtex (dividing Tekes), and tensile strength 4.1cN/dtex, elongation is
25%.
The above content is the further detailed description made for the present invention of specific preferred embodiment is combined, cannot recognize
Fixed specific implementation of the invention is only limited to these instructions.It for those of ordinary skill in the art, can be according to this hair
Bright technical solution and inventive concept makes corresponding change and substitution, and obtained using preparation method similar to the present invention
A kind of polyimide fine denier fiber, performance also must be the same, and all should be considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of polyimide fine denier fiber, which comprises the following steps:
Step 1: the preparation of polyamic acid spinning solution I
Be (0.9~1.1) using solvent A dissolution diamines, then in dianhydride and diamines molar ratio: dianhydride is added in 1 ratio thereto,
The total amount of dianhydride and diamines makes the solid content 15~30% of polyamic acid solution, 10~50 DEG C of temperature, reacts 8~20h, obtains
Polyamic acid spinning solution I, apparent viscosity are 50000~300000cp, after filtering 8~15h of vacuum defoamation；
Step 2: the preparation of the second component spinning solution II
Mixture A is added into solvent B and is configured to the second component spinning solution II, in the second component spinning solution II, mixture A
Mass percent be 1~50%, the solid content of the second component spinning solution II is 30~50%, stirs 8~15h, after filtering
Stand 6~12h deaeration；
The mixture A is selected from one or both of polyvinyl alcohol, polyvinylpyrrolidone；
Step 3: the preparation of bi-component mixing as-spun fibre
Polyamic acid spinning solution I is uniformly mixed with the second component spinning solution II, in the mixed solution, the polyamic acid
The mass percent of spinning solution I is 40~70%, and the mass percent of the second component spinning solution II is 60~30%, benefit
The mixed solution is sprayed with the porous spinneret that aperture is 0.04~0.1mm, obtains bi-component mixing as-spun fibre；
Step 4: the removal of the second component
The bi-component that step 3 obtains is mixed into as-spun fibre and is staged through dissolving tank 1, dissolving tank 2 and kitchen sink to remove the
Two components obtain polyamic acid as-spun fibre；
The mixed solution of deionized water and solvent C, in the mixed solution, the quality of deionized water are added in the dissolving tank 1
Percentage is 60~90%, and the mass percent of solvent C is 40~10%, and the temperature of mixed solution is controlled at 20~60 DEG C；
The mixed solution of deionized water and solvent D, in the mixed solution, the quality of deionized water are added in the dissolving tank 2
Percentage is 60~90%, and the mass percent of solvent C is 40~10%, and the temperature of mixed solution is controlled at 20~60 DEG C；
Deionized water is added in the kitchen sink, temperature is controlled at 20~60 DEG C；
Step 5: the post-processing of polyamic acid as-spun fibre
The polyamic acid as-spun fibre that step 4 obtains successively is gathered after drying, the heat treatment of segmentation warm area, stretch processing
Acid imide fine-denier fiber.
2. a kind of preparation method of polyimide fine denier fiber according to claim 1, which is characterized in that the solvent
A is identical as solvent B.
3. a kind of preparation method of polyimide fine denier fiber according to claim 1, which is characterized in that step 1
In, the solvent A is selected from dimethyl acetamide, dimethylformamide, N, N dimethyl pyrrolidones, dimethyl sulfoxide, tetrahydro furan
It one of mutters or a variety of.
4. a kind of preparation method of polyimide fine denier fiber according to claim 1, which is characterized in that step 1
In, the dianhydride is selected from equal benzene dianhydride, biphenyl dianhydride, two ether dianhydride of triphen, diphenyl ether dianhydride, thioether dianhydride, benzophenone two
One of acid anhydride, Bisphenol A Type Diether Dianhydride are a variety of.
5. a kind of preparation method of polyimide fine denier fiber according to claim 1, which is characterized in that step 1
In, the diamines is in 4,4 '-diaminodiphenyl ether diamines, p-phenylenediamine, two ether diamine of hexichol, two ether diamine of bisphenol A-type
It is one or more.
6. a kind of preparation method of polyimide fine denier fiber according to claim 1, which is characterized in that step 2
In, the solvent B is selected from dimethyl acetamide, dimethylformamide, N, N dimethyl pyrrolidones, dimethyl sulfoxide, tetrahydro furan
It one of mutters or a variety of.
7. a kind of preparation method of polyimide fine denier fiber according to claim 1, which is characterized in that step 4
In, the solvent C is selected from dimethyl acetamide, dimethylformamide, N, N dimethyl pyrrolidones, dimethyl sulfoxide, tetrahydro furan
It one of mutters or a variety of.
8. a kind of preparation method of polyimide fine denier fiber according to claim 1, which is characterized in that step 4
In, the solvent D is selected from dimethyl acetamide, dimethylformamide, N, N dimethyl pyrrolidones, dimethyl sulfoxide, tetrahydro furan
It one of mutters or a variety of.
9. a kind of preparation method of polyimide fine denier fiber according to claim 1, which is characterized in that step 5
Detailed process is as follows:
The polyamic acid as-spun fibre that step 4 is obtained is through 50~90 DEG C of dryings, 120~400 DEG C of heat treatments of segmentation warm area, 400
~500 DEG C of stretch processings, draw ratio are 0.5~2 times, obtain polyimide fine denier fiber.
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