CN105624819A - Preparation method of hydrophilic polyacrylonitrile-based carbon fiber precursor - Google Patents
Preparation method of hydrophilic polyacrylonitrile-based carbon fiber precursor Download PDFInfo
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Abstract
The invention relates to a preparation method of a hydrophilic polyacrylonitrile-based carbon fiber precursor, and mainly aims to solve the problems in the prior art that a polyacrylonitrile hydrophilic property is relatively poor, as a result, molding of spun precursors is too acute, surface grooves are relatively deep, and the degree of crystallinity is relatively low. The problems are relatively well solved through the technical scheme that the preparation method of the hydrophilic polyacrylonitrile-based carbon fiber precursor comprises the following steps: mixing a polymerized raw material polymerization component, an initiator and a solvent, and carrying out a polymerization reaction to obtain a spinning raw solution I; carrying out vacuum removal on residual monomers and bubbles from the spinning raw solution I, and filtering to obtain a high-hydrophilicity polyacrylonitrile copolymer spinning raw solution; and then carrying out spinneret plate extrusion, solidifying molding, water washing, drafting, oiling, drying compaction, steam drafting and steam heat setting on the spinning raw solution, and then winding to obtain the polyacrylonitrile-based carbon fiber precursor; and the method can be applied to industrial production of the carbon fiber precursor.
Description
Technical field
The present invention relates to the preparation of a kind of hydrophilic polypropylene itrile group carbon fibre precursor.
Background technology
Polyacrylonitrile (PAN) base carbon fibre is the new material developed rapidly in generation nineteen sixty, because of its there is light weight, the excellent properties such as specific strength is high, specific modulus is high, high temperature resistant, corrosion-resistant, wear-resisting, resisting fatigue, conduction, heat conduction, it is widely used in the military industries such as satellite, carrier rocket, tactical missile, spacecraft, it has also become indispensable material in aerospace industries. The features such as excellent carbon fiber precursor should have thermostability height, hole constructs less, few surface defects, compact structure, draftability are good.
Initial copolymer structure and performance determine structure and the performance of final carbon fiber. Therefore, set about from polyacrylonitrile synthesis, it is determined that the effect to polyacrylonitrile structure Yu performance of the different comonomers, the development carrying out polyacrylonitrile fibril is necessary. In order to obtain the polyacrylonitrile fibril of excellence it is necessary to select excellent properties spinning solution system, the hydrophilic wherein improving stock solution is exactly a main research direction. Improve the hydrophilicity of polyacrylonitrile matrix, be conducive to controlling the process of setting of nascent strand, make precursor in drafting process, infiltrate more abundant with WATER AS FLOW MEDIUM or steam, polyacrylonitrile can be played the effect of plasticising by water, such spun filament is easier to drafted, and precursor internal flaw is also more easy to makes up, is finally obtained in that the carbon fibre precursor that high strength dense is good.
But, up to the present people never find suitable method to improve the hydrophilic of polyacrylonitrile. Chinese patent CN201110005885.0,02130023.2 etc. all report the preparation first carrying out polyacrylonitrile copolymer, then in stock solution, ammonia is passed into, make stock solution pH in the middle of 8��10, the part carboxyl reaction making ammonia and itaconic acid generates ammonium salt, and this method is also the domestic hydrophilic method of change stock solution employed up at present. But the viscosity of polyacrylonitrile copolymer is relatively larger, it is a complicated heterogeneous reaction that ammonia and full-bodied stock solution will be made to react, and mass transfer is difficult and wayward, and the repeatability between batch experiment is poor.
Summary of the invention
Present invention mainly solves polyacrylonitrile hydrophilic in prior art poor, thus causing spun precursor molding excessively violent, the problem that surface grooves is relatively deep, degree of crystallinity is relatively low, the preparation method providing a kind of hydrophilic polypropylene itrile group carbon fibre precursor, this preparation method utilizes the solubility property that itaconic acid ammonium is excellent in water, itaconic acid aqueous ammonium is prepared high-hydrophilic acrylonitrile copolymer spinning solution as comonomer, thus the advantage that hydrophilic carbon fibre precursor is made in spinning.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: the preparation method of a kind of hydrophilic polypropylene itrile group carbon fibre precursor, comprises the following steps:
(1) prepared by stock solution: polymer raw copolymerization component, initiator are mixed with solvent, the aggregated spinning solution I that is obtained by reacting, spinning solution I through removed under reduced pressure residual monomer and bubble, be filtrated to get high-hydrophilic polyacrylonitrile copolymer spinning solution;
(2) by described polyacrylonitrile copolymer spinning solution through spinneret extrusion, coagulation forming, washing, drawing-off, oil, compacting by drying, steam drafting, steam heat sizing after receive silk obtain polyacrylonitrile base carbon fiber precursors;
Wherein, described copolymerization component includes acrylonitrile, first comonomer; Described first comonomer at least one in structure shown in formula I:
Formula I;
In formula I, M, M' are independently chosen from least one in alkali metal, ammonium; And described first comonomer adds with the form of its aqueous solution, the mass ratio of first comonomer and water is 1:(0.1��5).
In technique scheme, in described high-hydrophilic polyacrylonitrile copolymer spinning solution, polyacrylonitrile copolymer molecular weight is 8��180,000, and molecular weight distribution is 1��3; Described high-hydrophilic polyacrylonitrile copolymer dope viscosity is 40��120Pa s at 60 DEG C; The contact angle of the co-polymer membrane that described high-hydrophilic polyacrylonitrile copolymer spinning solution is made and water is 40 �㡫55 ��.
In technique scheme, described copolymerization component is it is also preferred that include second comonomer.
In technique scheme, the proportioning of described polymer raw is counted by weight, copolymerization component is preferably 15��35 parts, wherein acrylonitrile is preferably 13��33 parts, first comonomer is preferably 1��4 part, second comonomer is preferably 1��4 part, and solvent is preferably 65��84 parts, and initiator amount is preferably the 0.2��1% of copolymerization component gross weight; The reaction temperature of described polyreaction is preferably 30��80 DEG C, more preferably 40��70 DEG C, described de-single mode adopting the de-list of vacuum; Described filter type is Multi-channel filtering precision respectively 2-5 ��m.
At least one in technique scheme, in described first comonomer more preferably sodium itaconate, itaconic acid potassium or itaconic acid ammonium; First comonomer preferably adds with the form of its aqueous solution, is namely first dissolved in the water by itaconate, and the mass ratio of first comonomer and water is more preferably 1:(1��3).
In technique scheme, described second comonomer, solvent, initiator can be various comonomer (being different from first comonomer) commonly used in the art, solvent and initiator, and this can be carried out conventional selection by those skilled in the art; Such as but do not limit described initiator selected from azo-initiator, more than at least one or two in azodiisobutyronitrile, AMBN and 2,2'-Azobis(2,4-dimethylvaleronitrile); Described solvent preferably is selected from least one in dimethyl acetylamide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and dimethyl sulfoxide; Described second comonomer preferably is selected from structure shown in formula II, formula III, at least one in acrylamide, acryloyl amidoxime, hydroxylethyl nitrile, �� chloroacrylonitrile or N-[2-(2-methyl-4-oxopentyl); As having itaconic acid, ��-itaconic acid n-butyl etc. selected from formula I, have acrylic acid, acrylic acid methyl ester., methyl methacrylate, ethyl methacrylate, isobutyl group acrylic acid etc. selected from formula II, more preferably itaconic acid, ��-itaconic acid n-butyl.
Wherein, R1��R2��R3��R4It is independently chosen from H or C1��C4Alkyl.
In technique scheme, polyacrylonitrile base carbon fiber precursors spinning technique in described step (2) can adopt those skilled in the art the common process of ripe prior art, such as wet spinning, dry-jet wet-spinning etc., the key of the present invention does not lie in this, and the common process of prior art also can meet the object of the invention. But preferably can be undertaken by following technical scheme.
In technique scheme, described coagulation forming preferably employs multistage solidification mode, more preferably through the above coagulating bath of twice, coagulating bath medium is preferably the aqueous solution of dimethyl sulfoxide, the concentration of coagulating bath preferably employs the solidification of ladder concentration, concentration is preferably 10%-80%, the concentration of first road coagulating bath is preferably no greater than the concentration of follow-up coagulating bath, the temperature of coagulating bath is both preferably 20��70 DEG C, first road coagulating bath is preferably negative drawing-off, draw ratio is preferably-5%��-50%, and the draw ratio of follow-up solidification is both preferably 1��3. In technique scheme, described coagulating bath concentration more preferably 20%��70%; The temperature of described coagulating bath is it is preferred that 30��60 DEG C; The draw ratio of first road coagulating bath more preferably-20%��-40%.
In technique scheme, the drawing-off described in step (2) is preferably multiple tracks hot water drawing-off, more preferably the above hot water drawing-off of twice; Per pass hot water drawing-off preferably employs 60��90 DEG C of hot water and carries out drawing-off, and hot water draw ratio is both preferably 1��3 times.
In technique scheme, the washing described in step (2) is preferably multiple tracks washing, more preferably more than twice wash; Per pass washing preferably employs 40��80 DEG C of washings, it is preferred to use the mode of ladder-elevating temperature, and first road washing temperature is preferably not higher than follow-up washing temperature; Water rinses does not preferably carry out drawing-off.
In technique scheme, the oil preparation adopted that oils described in step (2) is preferably ammonia modified silicon oil, and the concentration of oil preparation is preferably 0.1wt%��1wt%; The temperature of described compacting by drying is preferably 60��160 DEG C, more preferably 40��140 DEG C; The pressure of described steam drafting is preferably 0.1-0.4MPa, and draw ratio is preferably 1��4 times; Described thermal finalization is preferably steam heat sizing, and the pressure of steam heat sizing is preferably 0.1-0.3MPa.
In technique scheme, the method for testing of stock solution viscosity is use rotational rheometer, shear rate 0.1s-1��10s-1, and test condition includes adding shears and be not added with pre-shearing two kinds in advance; The method of testing of stock solution viscosity-average molecular weight is for using dark type viscometer to test, and test condition is: temperature 20 DEG C��60 DEG C, and solvent adopts and adds electrolytical dimethylformamide, and electrolyte selects at least one in lithium bromide or sodium nitrate; The method of testing of stock solution molecular weight distribution (Mw/Mn) is tested for using high-temperature gel permeation chromatography; The test condition of stock solution molecular weight distribution (Mw/Mn) is: temperature 50 C��150 DEG C, and mobile phase is selected and added electrolytical dimethylformamide, and electrolyte selects at least one in lithium bromide or sodium nitrate.
In technique scheme, filament number is tested according to standard GB/T/T14335-2008, and filament strength and monofilament modulus are tested according to standard GB/T/T14337-2008, and precursor density is tested by density gradient instrument.
Although it is the most frequently used at present comonomer that the present invention selects itaconic acid aqueous ammonium to be because itaconic acid as comonomer, but its hydrophilic is bad, the follow-up words carrying out ammonification, operation inconvenience, technique is difficult to control to, between batch, difference is big, so to introduce the comonomer itaconate with hydrophilic group, but itaconate is insoluble in dimethyl sulfoxide, when 60 DEG C, dissolubility is only 0.2wt%, dissolution velocity is also very slow, limit itaconic acid ammonium as comonomer use in dimethyl sulfoxide system, so being currently mainly used in aqueous deposited polymerization, the present invention utilizes itaconate to be first dissolved in water by itaconate, again itaconate aqueous solution is added in polymeric kettle as Third monomer, namely in system, introduce hydrophilic radical, solve again the problem that itaconate is insoluble in dimethyl sulfoxide, simultaneously because the dissolubility that itaconate is in water is very excellent, so the water introduced in system is less than 1000ppm, any impact is not had for copolyreaction, the hydrophilic spinning solution of excellent performance can be obtained, it is few by surface grooves can be obtained after spinning moulding, high intensity, the hydrophilic carbon fibre precursor that compactness is good.
Adopting the solution of the present invention, the polyacrylonitrile carbon fiber precursor obtained, precursor fiber number is 0.6��1.2dtex, and filament strength is 7��10cN/dtex, and protonema density is 1.17��1.19, achieves good technique effect.
The present invention is further elaborated by the examples below:
Detailed description of the invention
[embodiment 1]
1, prepared by stock solution: join in reactor by 98g through the acrylonitrile (AN) of distillation, 1.5g itaconic acid (IA), sodium itaconate aqueous solution (being dissolved in 1.5g water by sodium itaconate 1.5g), 0.6g azodiisobutyronitrile (AIBN), 400g dimethyl acetylamide; with under nitrogen protection; react 20 hours under the steady temperature of 60 DEG C; then spinning liquid is after removed under reduced pressure residual monomer and bubble, obtains polyacrylonitrile copolymer spinning solution. After tested, molecular weight is 100870, and molecular weight distribution is 2.76, and viscosity is 58Pa S at 60 DEG C, and the contact angle of the co-polymer membrane that this stock solution is made and water is 42.7 ��
2, coagulation forming: spinning solution is after dosing pump metering, again passing by 3 ��m of filtrations, entering the 1st road coagulating bath, coagulation bath temperature 20 DEG C by spinning head after being extruded, concentration is 50%, draw ratio is-30%, 2nd road coagulating bath is 40 DEG C, and concentration is 40%, and draw ratio is 100%, 3rd road coagulating bath is 60 DEG C, concentration is 30%, and draw ratio is 105%, obtains as-spun fibre.
3, drawing-off and washing: as-spun fibre by, after 3 roads solidifications, carrying out hot water 3 road drawing-off, 3 road hot water drawing temperatures respectively 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple respectively 1.2,1.4 and 2.. After 3 road hot water drawing-offs, strand carries out 9 road washings, adopts the mode of ladder-elevating temperature, and 1-3 road washing temperature is 50 DEG C, and 4-6 road washing temperature is 60 DEG C, and 7-9 road washing temperature is 70 DEG C, and water rinses does not carry out drawing-off.
4, oil and compacting by drying: fiber step 3 obtained carries out carrying out compacting by drying after 1 road oils, and temperature is 90 DEG C, followed by once oiling, after oiling, carries out the 2nd road compacting by drying, and the temperature of compacting by drying is 120 DEG C.
5, steam drafting: fiber step 4 obtained carries out steam drafting, the pressure of steam drafting is 0.2Mpa, and draw ratio is 2 times.
6, steam heat sizing and receipts silk: fiber step 5 obtained receives silk after carrying out steam heat sizing, obtains high-performance carbon fibre precursor, and the pressure of steam heat sizing is 0.2Mpa.
The fiber number of gained precursor is 1.21dtex, and filament strength is 8cN/dtex, and precursor density is 1.178.
[embodiment 2]
1, prepared by stock solution: by 121g through the acrylonitrile (AN) of distillation, 1.25g itaconic acid (IA), itaconic acid aqueous solutions of potassium (being dissolved in 1.5g water by itaconic acid potassium 1.5g), 0.75g azodiisobutyronitrile (AIBN), 376gN; dinethylformamide joins in reactor; under helium is protected; react 24 hours under the steady temperature of 60 DEG C; then spinning liquid is after removed under reduced pressure residual monomer and bubble, obtains polyacrylonitrile copolymer spinning solution. After tested, molecular weight is 145067, and molecular weight distribution is 2.61, and viscosity is 87Pa S at 60 DEG C, and the contact angle of the co-polymer membrane that this stock solution is made and water is 52.5 ��.
All the other steps are according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength is 8.3cN/dtex, and precursor density is 1.181.
[embodiment 3]
1, prepared by stock solution: by 146g through the acrylonitrile (AN) of distillation, 2g itaconic acid (IA), itaconic acid aqueous ammonium (being dissolved in 5g water by itaconic acid ammonium 3g), 0.9g azodiisobutyronitrile (AIBN) and 350gN; N-dimethyl acetylamide joins in reactor; under argon shield; react 26 hours under the steady temperature of 60 DEG C; then spinning liquid is after removed under reduced pressure residual monomer and bubble, obtains polyacrylonitrile copolymer spinning solution. After tested, molecular weight is 152560, and molecular weight distribution is 2.91, and viscosity is 92Pa S at 60 DEG C, and the contact angle of the co-polymer membrane that this stock solution is made and water is 45.6 ��
All the other steps are according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength is 8.1cN/dtex, and precursor density is 1.183.
[embodiment 4]
1, prepared by stock solution: join in reactor by 120g through the acrylonitrile (AN) of distillation, 3g itaconic acid (IA), sodium itaconate aqueous solution (being dissolved in 4g water by sodium itaconate 2g), 0.5g azodiisobutyronitrile (AIBN) and 375g dimethyl sulfoxide (DMSO); under nitrogen protection; react 28 hours under the steady temperature of 50 DEG C; then spinning liquid is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution. After tested, molecular weight is 148567, and molecular weight distribution is 2.74, and viscosity is 77Pa S at 60 DEG C, and the contact angle of the co-polymer membrane that this stock solution is made and water is 50.1 ��
All the other steps are according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength is 9.3cN/dtex, and precursor density is 1.185.
[embodiment 5]
1, prepared by stock solution: by 120g through the acrylonitrile (AN) of distillation, 4g itaconic acid (IA), itaconic acid aqueous solutions of potassium (being dissolved in 3g water by itaconic acid potassium 1g), 0.5g azodiisobutyronitrile (AIBN), 375gN; dinethylformamide joins in reactor; under nitrogen protection; react 32 hours under the steady temperature of 60 DEG C; then spinning liquid is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution. After tested, molecular weight is 140567, and molecular weight distribution is 2.76, and viscosity is 62Pa S at 60 DEG C, and the contact angle of the co-polymer membrane that this stock solution is made and water is 54.6 ��.
All the other steps are according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength is 9.9cN/dtex, and precursor density is 1.171.
[embodiment 6]
1, prepared by stock solution: according to the stock solution preparation process of embodiment 1.
2, coagulation forming: spinning solution is after dosing pump metering, again passing by 3 ��m of filtrations, entering the 1st road coagulating bath, coagulation bath temperature 30 DEG C by spinning head after being extruded, concentration is 60%, draw ratio is-40%, 2nd road coagulating bath is 50 DEG C, and concentration is 30%, and draw ratio is 100%, 3rd road coagulating bath is 60 DEG C, concentration is 20%, and draw ratio is 105%, obtains as-spun fibre.
All the other steps are according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength is 7.9cN/dtex, and precursor density is 1.176.
[embodiment 7]
1, prepared by stock solution: according to the stock solution preparation process of embodiment 1.
2, coagulation forming: spinning solution, after dosing pump metering, again passing by 3 ��m of filtrations, enters the 1st road coagulating bath, coagulation bath temperature 40 DEG C by spinning head after being extruded, concentration is 65%, and draw ratio is-50%, and the 2nd road coagulating bath is 60 DEG C, concentration is 30%, and draw ratio is 100%, and the 3rd road coagulating bath is 60 DEG C, concentration is 20%, draw ratio is 115%, and the 4th road coagulating bath is 70 DEG C, and concentration is 20%, draw ratio is 150%, obtains as-spun fibre.
All the other steps are according to embodiment 1.
The fiber number of gained precursor is 1.15dtex, and filament strength is 7.1cN/dtex, and precursor density is 1.176.
[embodiment 8]
1, prepared by stock solution: according to the stock solution preparation process of embodiment 1.
2, coagulation forming: spinning solution is after dosing pump metering, again passing by 3 ��m of filtrations, entering the 1st road coagulating bath, coagulation bath temperature 50 DEG C by spinning head after being extruded, concentration is 65%, draw ratio is-30%, 2nd road coagulating bath is 60 DEG C, and concentration is 20%, and draw ratio is 100%, 3rd road coagulating bath is 70 DEG C, concentration is 10%, and draw ratio is 120%, obtains as-spun fibre.
All the other steps are according to embodiment 1.
The fiber number of gained precursor is 1.05dtex, and filament strength is 8.1cN/dtex, and precursor density is 1.178.
[embodiment 9]
1, prepared by stock solution: according to the stock solution preparation process of embodiment 1.
2, coagulation forming: spinning solution is after dosing pump metering, again passing by 3 ��m of filtrations, entering the 1st road coagulating bath, coagulation bath temperature 60 DEG C by spinning head after being extruded, concentration is 75%, draw ratio is-35%, 2nd road coagulating bath is 70 DEG C, and concentration is 30%, and draw ratio is 110%, 3rd road coagulating bath is 70 DEG C, concentration is 10%, and draw ratio is 120%, obtains as-spun fibre.
3, drawing-off and washing: as-spun fibre by, after 3 roads solidifications, carrying out hot water 3 road drawing-off, 3 road hot water drawing temperatures respectively 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple respectively 1.2,1.2 and 1.2. After 3 road hot water drawing-offs, strand carries out 9 road washings, adopts the mode of ladder-elevating temperature, and 1-3 road washing temperature is 50 DEG C, and 4-6 road washing temperature is 60 DEG C, and 7-9 road washing temperature is 70 DEG C, and water rinses does not carry out drawing-off.
4, oil and compacting by drying: fiber step 3 obtained carries out carrying out compacting by drying after 1 road oils, and temperature is 90 DEG C, followed by once oiling, after oiling, carries out the 2nd road compacting by drying, and the temperature of compacting by drying is 120 DEG C.
5, steam drafting: fiber step 4 obtained carries out steam drafting, the pressure of steam drafting is 0.15Mpa, and draw ratio is 1.6 times.
6, steam heat sizing and receipts silk: fiber step 5 obtained receives silk after carrying out steam heat sizing, obtains high-performance carbon fibre precursor, and the pressure of steam heat sizing is 0.2Mpa.
The fiber number of gained precursor is 1.21dtex, and filament strength is 8.5cN/dtex, and precursor density is 1.178.
[embodiment 10]
1, prepared by stock solution: according to the stock solution preparation process of embodiment 1.
2, coagulation forming: spinning solution is after dosing pump metering, again passing by 3 ��m of filtrations, entering the 1st road coagulating bath, coagulation bath temperature 60 DEG C by spinning head after being extruded, concentration is 75%, draw ratio is-35%, 2nd road coagulating bath is 70 DEG C, and concentration is 30%, and draw ratio is 110%, 3rd road coagulating bath is 70 DEG C, concentration is 10%, and draw ratio is 120%, obtains as-spun fibre.
3, drawing-off and washing: as-spun fibre by, after 3 roads solidifications, carrying out hot water 3 road drawing-off, 3 road hot water drawing temperatures respectively 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple respectively 1.4,1.6 and 1.8. After 3 road hot water drawing-offs, strand carries out 9 road washings, adopts the mode of ladder-elevating temperature, and 1-4 road washing temperature is 50 DEG C, and 5-8 road washing temperature is 60 DEG C, and 9-12 road washing temperature is 70 DEG C, and water rinses does not carry out drawing-off.
4, oil and compacting by drying: fiber step 3 obtained carries out carrying out compacting by drying after 1 road oils, and temperature is 80 DEG C, followed by once oiling, after oiling, carries out the 2nd road compacting by drying, and the temperature of compacting by drying is 140 DEG C.
5, steam drafting: fiber step 4 obtained carries out steam drafting, the pressure of steam drafting is 0.4Mpa, and draw ratio is 3 times.
6, steam heat sizing and receipts silk: fiber step 5 obtained receives silk after carrying out steam heat sizing, obtains high-performance carbon fibre precursor, and the pressure of steam heat sizing is 0.2Mpa.
The fiber number of gained precursor is 0.75dtex, and filament strength is 8.8cN/dtex, and precursor density is 1.188.
[embodiment 11]
1, prepared by stock solution: according to the stock solution preparation process of embodiment 1.
2, coagulation forming: spinning solution is after dosing pump metering, again passing by 3 ��m of filtrations, entering the 1st road coagulating bath, coagulation bath temperature 50 DEG C by spinning head after being extruded, concentration is 75%, draw ratio is-30%, 2nd road coagulating bath is 50 DEG C, and concentration is 30%, and draw ratio is 105%, 3rd road coagulating bath is 60 DEG C, concentration is 15%, and draw ratio is 110%, obtains as-spun fibre.
3, drawing-off and washing: as-spun fibre by, after 3 roads solidifications, carrying out hot water 3 road drawing-off, 3 road hot water drawing temperatures respectively 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple respectively 1.6,2 and 1.8. After 3 road hot water drawing-offs, strand carries out 9 road washings, adopts the mode of ladder-elevating temperature, and 1-4 road washing temperature is 50 DEG C, and 5-8 road washing temperature is 60 DEG C, and 9-12 road washing temperature is 70 DEG C, and water rinses does not carry out drawing-off.
4, oil and compacting by drying: fiber step 3 obtained carries out carrying out compacting by drying after 1 road oils, and temperature is 85 DEG C, followed by once oiling, after oiling, carries out the 2nd road compacting by drying, and the temperature of compacting by drying is 155 DEG C.
5, steam drafting: fiber step 4 obtained carries out steam drafting, the pressure of steam drafting is 0.4Mpa, and draw ratio is 2.5 times.
6, steam heat sizing and receipts silk: fiber step 5 obtained receives silk after carrying out steam heat sizing, obtains high-performance carbon fibre precursor, and the pressure of steam heat sizing is 0.2Mpa.
The fiber number of gained precursor is 0.75dtex, and filament strength is 10cN/dtex, and precursor density is 1.188.
[embodiment 12]
1, prepared by stock solution: according to the stock solution preparation process of embodiment 1.
2, coagulation forming: spinning solution is after dosing pump metering, again passing by 3 ��m of filtrations, entering the 1st road coagulating bath, coagulation bath temperature 50 DEG C by spinning head after being extruded, concentration is 75%, draw ratio is-30%, 2nd road coagulating bath is 50 DEG C, and concentration is 30%, and draw ratio is 105%, 3rd road coagulating bath is 60 DEG C, concentration is 15%, and draw ratio is 110%, obtains as-spun fibre.
3, drawing-off and washing: as-spun fibre by, after 3 roads solidifications, carrying out hot water 3 road drawing-off, 3 road hot water drawing temperatures respectively 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple respectively 1.8,1.8 and 2. After 3 road hot water drawing-offs, strand carries out 9 road washings, adopts the mode of ladder-elevating temperature, and 1-3 road washing temperature is 50 DEG C, and 4-6 road washing temperature is 60 DEG C, and 7-9 road washing temperature is 70 DEG C, and water rinses does not carry out drawing-off.
4, oil and compacting by drying: fiber step 3 obtained carries out carrying out compacting by drying after 1 road oils, and temperature is 85 DEG C, followed by once oiling, after oiling, carries out the 2nd road compacting by drying, and the temperature of compacting by drying is 155 DEG C.
5, steam drafting: fiber step 4 obtained carries out steam drafting, the pressure of steam drafting is 0.4Mpa, and draw ratio is 2 times.
6, steam heat sizing and receipts silk: fiber step 5 obtained receives silk after carrying out steam heat sizing, obtains high-performance carbon fibre precursor, and the pressure of steam heat sizing is 0.2Mpa.
The fiber number of gained precursor is 0.75dtex, and filament strength is 7cN/dtex, and precursor density is 1.185.
[comparative example 1]
1, prepared by stock solution: join in reactor by 98g through the acrylonitrile (AN) of distillation, 1.5g itaconic acid (IA), sodium itaconate 1.5g, 0.6g azodiisobutyronitrile (AIBN), 400g dimethyl acetylamide, owing to sodium itaconate dissolubility in dimethyl sulfoxide is too low, so there being part sodium itaconate not to be completely dissolved, cause spinning solution uneven.
[comparative example 2]
1, prepared by stock solution: by 97g through the acrylonitrile (AN) of distillation, 3g itaconic acid (IA), 0.6g azodiisobutyronitrile (AIBN), 380gN; dinethylformamide joins in reactor; under nitrogen protection; react 20 hours under the steady temperature of 60 DEG C; then spinning liquid is after removed under reduced pressure residual monomer and bubble, obtains novel acrylonitrile copolymer spinning solution. After tested, molecular weight is 112560, and molecular weight distribution is 2.70, and viscosity is 167Pa S at 60 DEG C, and the contact angle of the co-polymer membrane that this stock solution is made and water is 58.1 ��
2, coagulation forming: spinning solution is after dosing pump metering, again passing by 3 ��m of filtrations, entering the 1st road coagulating bath, coagulation bath temperature 60 DEG C by spinning head after being extruded, concentration is 75%, draw ratio is-30%, 2nd road coagulating bath is 60 DEG C, and concentration is 30%, and draw ratio is 105%, 3rd road coagulating bath is 60 DEG C, concentration is 15%, and draw ratio is 110%, obtains as-spun fibre.
3, drawing-off and washing: as-spun fibre by, after 3 roads solidifications, carrying out hot water 3 road drawing-off, 3 road hot water drawing temperatures respectively 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple respectively 1.6,1.6 and 1.8. After 3 road hot water drawing-offs, strand carries out 9 road washings, adopts the mode of ladder-elevating temperature, and 1-3 road washing temperature is 50 DEG C, and 4-6 road washing temperature is 60 DEG C, and 7-9 road washing temperature is 70 DEG C, and water rinses does not carry out drawing-off.
4, oil and compacting by drying: fiber step 3 obtained carries out carrying out compacting by drying after 1 road oils, and temperature is 85 DEG C, followed by once oiling, after oiling, carries out the 2nd road compacting by drying, and the temperature of compacting by drying is 125 DEG C.
5, steam drafting: fiber step 4 obtained carries out steam drafting, the pressure of steam drafting is 0.4Mpa, and draw ratio is 2 times.
6, steam heat sizing and receipts silk: fiber step 5 obtained receives silk after carrying out steam heat sizing, obtains high-performance carbon fibre precursor, and the pressure of steam heat sizing is 0.2Mpa.
The fiber surface groove prepared is serious, and compact structure is poor, and the fiber number of gained precursor is 1.21dtex, and filament strength is 5.3cN/dtex, and precursor density is 1.173.
Claims (10)
1. a preparation method for hydrophilic polypropylene itrile group carbon fibre precursor, comprises the following steps:
(1) prepared by stock solution: polymer raw copolymerization component, initiator are mixed with solvent, the aggregated spinning solution I that is obtained by reacting, and spinning solution I is through removed under reduced pressure residual monomer and bubble, the polyacrylonitrile copolymer spinning solution being filtrated to get high-hydrophilic;
(2) by described polyacrylonitrile copolymer spinning solution through spinneret extrusion, coagulation forming, washing, drawing-off, oil, compacting by drying, steam drafting, steam heat sizing after receive silk obtain polyacrylonitrile base carbon fiber precursors;
Wherein, described copolymerization component includes acrylonitrile, first comonomer; Described first comonomer at least one in structure shown in formula I:
In formula I, M, M' are independently chosen from least one in alkali metal, ammonium; And described first comonomer adds with the form of its aqueous solution, the mass ratio of first comonomer and water is 1:(0.1��5).
2. the preparation method of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that described copolymerization component also includes the second comonomer.
3. the preparation method of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 2, it is characterized in that in the preparation of described stock solution, the proportioning of polymer raw is counted by weight, described acrylonitrile is 13��33 parts, first comonomer is 1��4 part, second comonomer is 1��4 part, and solvent is 65��84 parts, and initiator amount is the 0.2��1% of copolymerization component gross weight.
4. the preparation method of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that the reaction temperature of described polyreaction is 30��80 DEG C, it is preferable that 40��70 DEG C, de-single mode adopting the de-list of vacuum.
5. the preparation of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that described second comonomer is at least one in sodium itaconate, itaconic acid potassium, itaconic acid ammonium.
6. the preparation of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterized in that described coagulation forming adopts multistage solidification mode, through the above coagulating bath of twice, coagulating bath medium is the aqueous solution of dimethyl sulfoxide, the concentration of coagulating bath adopts the solidification of ladder concentration, concentration is 10%-80%, the concentration of first road coagulating bath is not more than the concentration of follow-up coagulating bath, the temperature of coagulating bath all controls to be 20��70 DEG C, first road coagulating bath is negative drawing-off, draw ratio is-5%��-50%, and the draw ratio of follow-up solidification is 1��3.
7. the preparation of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that described drawing-off is multiple tracks hot water drawing-off, per pass all adopts 60��90 DEG C of hot water to carry out drawing-off, and hot water draw ratio all controls at 1��3 times.
8. the preparation of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterized in that described washing is multiple tracks washing, per pass all adopts 40��80 DEG C of washings, adopts the mode of ladder-elevating temperature, first road washing temperature is not more than follow-up washing temperature, and water rinses does not carry out drawing-off.
9. the preparation of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that described in oil adopt oil preparation be ammonia modified silicon oil, the concentration of oil preparation is 0.1wt%��1wt%; The temperature of described compacting by drying is 60��160 DEG C, it is preferred to 40��140 DEG C.
10. the preparation of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that the pressure of steam drafting is 0.1-0.4MPa, and draw ratio is 1��4 times.
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