CN105624819B - The preparation method of hydrophilic polypropylene itrile group carbon fibre precursor - Google Patents
The preparation method of hydrophilic polypropylene itrile group carbon fibre precursor Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of hydrophilic polypropylene itrile group carbon fibre precursor, it is poor mainly to solve polyacrylonitrile hydrophily in the prior art, so as to cause that spun precursor shaping is excessively violent, and surface grooves are compared with the problem of deep, crystallinity is relatively low.The present invention comprises the following steps by using the preparation method of hydrophilic polypropylene itrile group carbon fibre precursor：Polymer raw copolymerization component, initiator are mixed with solvent, aggregated reaction obtains spinning solution I, and spinning solution I is through removed under reduced pressure residual monomer and bubble, the polyacrylonitrile copolymer spinning solution that high-hydrophilic is obtained by filtration；Then extrude by spinneret, coagulation forming, washing, drawing-off, oil, compacting by drying, steam drafting, silk is received after steam thermal finalization obtain the technical solutions of polyacrylonitrile base carbon fiber precursors and preferably resolve the problem, in the industrial production for the carbon fibre precursor that can be used for.
Description
Technical field
The present invention relates to a kind of preparation of hydrophilic polypropylene itrile group carbon fibre precursor.
Background technology
Polyacrylonitrile (PAN) base carbon fibre is the new material that develops rapidly of generation nineteen sixty, because its with light weight,
The excellent properties such as specific strength height, specific modulus height, high temperature resistant, corrosion-resistant, wear-resisting, antifatigue, conductive, heat conduction, are widely used in
The military industries such as satellite, carrier rocket, tactical missile, spaceship, it has also become indispensable material in aerospace industries.
Excellent carbon fiber precursor should have heat resistance is high, hole constructs less, few surface defects, compact structure, draftability are good etc.
Feature.
Initial copolymer structure and performance determines the structure and performance of final carbon fiber.Therefore, closed from polyacrylonitrile
Into setting about, effect of the different comonomers to polyacrylonitrile structure and performance is determined, carrying out the development of polyacrylonitrile fibril is
It is highly desirable.Excellent polyacrylonitrile fibril is it is necessary to select excellent properties spinning solution system in order to obtain, wherein improving
The hydrophily of stoste is exactly a main research direction.Improve the hydrophilicity of polyacrylonitrile matrix, it is nascent to be conducive to control
The process of setting of strand, makes precursor in drafting process, and more abundant with WATER AS FLOW MEDIUM or vapor infiltration, water can play polyacrylonitrile
To the effect of plasticising, such spun filament is easier to be drafted, and precursor internal flaw is also more easy to make up, can finally obtain high intensity
The good carbon fibre precursor of compactness.
However, up to the present people never find suitable method to improve the hydrophily of polyacrylonitrile.China
Patent CN201110005885.0,02130023.2 etc. all report the preparation for first carrying out polyacrylonitrile copolymer, then to original
Ammonia is passed through in liquid, makes stoste pH among 8~10 so that the part carboxyl reaction generation ammonium salt of ammonia and itaconic acid, this side
Method is also the current domestic most commonly used change hydrophilic method of stoste.But the viscosity of polyacrylonitrile copolymer is bigger,
It is a complicated heterogeneous reaction make it that ammonia carries out reaction with highly viscous stoste, and mass transfer is difficult and not easy to control, batch
It is less reproducible between experiment.
The content of the invention
Present invention mainly solves polyacrylonitrile hydrophily in the prior art is poor, so as to cause spun precursor shaping excessively
Acutely, surface grooves are compared with the problem of deep, crystallinity is relatively low, there is provided a kind of preparation of hydrophilic polypropylene itrile group carbon fibre precursor
Method, the preparation method is using itaconic acid ammonium excellent solubility property in water, using itaconic acid aqueous ammonium as comonomer
High-hydrophilic acrylonitrile copolymer spinning solution is prepared, so that the advantages of hydrophilic carbon fibre precursor is made in spinning.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of hydrophilic polypropylene itrile group carbon is fine
The preparation method of precursor is tieed up, is comprised the following steps：
(1) prepared by stoste：Polymer raw copolymerization component, initiator are mixed with solvent, aggregated reaction obtains spinning original
Liquid I, spinning solution I through removed under reduced pressure residual monomer and bubble, high-hydrophilic polyacrylonitrile copolymer spinning solution is obtained by filtration；
(2) by the polyacrylonitrile copolymer spinning solution by spinneret extrusion, coagulation forming, washing, drawing-off, on
Silk is received after oil, compacting by drying, steam drafting, steam thermal finalization and obtains polyacrylonitrile base carbon fiber precursors；
Wherein, the copolymerization component includes acrylonitrile, the first comonomer；First comonomer is selected from formula (I) institute
Show at least one of structure：
Formula (I)；
M, M' are independently chosen from least one of alkali metal, ammonium in formula (I)；And first comonomer is with its water
The mass ratio of the form addition of solution, the first comonomer and water is 1:(0.1~5).
In above-mentioned technical proposal, polyacrylonitrile copolymer molecule in the high-hydrophilic polyacrylonitrile copolymer spinning solution
Measure as 8~180,000, molecular weight distribution is 1~3；The high-hydrophilic polyacrylonitrile copolymer dope viscosity is at 60 DEG C
40~120Pas；The contact angle of co-polymer membrane and water made of the high-hydrophilic polyacrylonitrile copolymer spinning solution is
40 °~55 °.
In above-mentioned technical proposal, the copolymerization component further preferably includes second comonomer.
In above-mentioned technical proposal, the proportioning of the polymer raw is counted in parts by weight, and copolymerization component is preferably 15~35 parts,
Wherein acrylonitrile is preferably 13~33 parts, and the first comonomer is preferably 1~4 part, and the second comonomer is preferably 1~4 part, molten
Agent is preferably 65~84 parts, and initiator amount is preferably the 0.2~1% of copolymerization component gross weight；The reaction of the polymerisation
Temperature is preferably 30~80 DEG C, more preferably 40~70 DEG C, the de- list using vacuum take off it is single by the way of；The filter type
It it is respectively 2-5 μm for Multi-channel filtering precision.
In above-mentioned technical proposal, first comonomer is more preferably sodium itaconate, itaconic acid potassium or itaconic acid
At least one of ammonium；First comonomer adds preferably in the form of its aqueous solution, i.e., first itaconate is dissolved in the water,
The mass ratio of first comonomer and water is more preferably 1:(1~3).
In above-mentioned technical proposal, second comonomer, solvent, initiator can be that various copolymerization commonly used in the art are single
Body (being different from the first comonomer), solvent and initiator, those skilled in the art can be to this progress conventional selections；Such as but
The initiator is not limited and is selected from azo-initiator, such as selected from two different heptan of azodiisobutyronitrile, azobisisovaleronitrile and azo
At least one of nitrile is two or more；The solvent preferably is selected from dimethylacetylamide, N,N-dimethylformamide, N, N- diformazans
At least one of yl acetamide and dimethyl sulfoxide；Second comonomer preferably is selected from formula (II), in structure shown in formula (III),
At least one of acrylamide, acryloyl amidoxime, hydroxylethyl nitrile, α chloroacrylonitriles or Diacetone Acrylamide；Such as choosing
There are itaconic acid, β-itaconic acid n-butyl etc. from formula (I), have acrylic acid, methyl acrylate, methyl methacrylate selected from formula (II)
Ester, ethyl methacrylate, isobutyl group acrylic acid etc., more preferably itaconic acid, β-itaconic acid n-butyl.
Wherein, R1、R2、R3、R4It is independently chosen from H or C1~C4Alkyl.
In above-mentioned technical proposal, the polyacrylonitrile base carbon fiber precursors spinning technique in the step (2) can use this
Field technology personnel the ripe prior art common process, such as wet spinning, dry-jet wet-spinning etc., it is of the invention it is crucial not
It is this, the common process of the prior art can also meet the object of the invention.But preferably can by following technical solution into
OK.
In above-mentioned technical proposal, the coagulation forming is preferably using multistage solidification mode, more preferably through more than twice solidifying
Bath, coagulating bath medium are preferably the aqueous solution of dimethyl sulfoxide (DMSO), and the concentration of coagulating bath is preferably solidified using ladder concentration, and concentration is excellent
Elect 10%-80% as, the concentration of first road coagulating bath is preferably no greater than the concentration of follow-up coagulating bath, and the temperature of coagulating bath is both preferably
20~70 DEG C, first road coagulating bath is preferably negative drawing-off, and draw ratio is preferably -5%~-50%, and the draw ratio subsequently solidified is excellent
Elect 1~3 as.In above-mentioned technical proposal, the solidification bath concentration is more preferably 20%~70%；The temperature of the coagulating bath
Further preferred 30~60 DEG C；The draw ratio of first road coagulating bath is more preferably -20%~-40%.
In above-mentioned technical proposal, the drawing-off described in step (2) is preferably multiple tracks hot water drawing-off, more preferably more than twice
Hot water drawing-off；The drawing-off of per pass hot water preferably carries out drawing-off using 60~90 DEG C of hot water, and hot water draw ratio is both preferably 1~3 times.
In above-mentioned technical proposal, the washing described in step (2) is preferably multiple tracks washing, more preferably more than twice is washed；
Per pass washing is preferably using 40~80 DEG C of washings, it is preferred to use the mode of ladder-elevating temperature, first road washing temperature are preferably not higher than
Follow-up washing temperature；Water rinses are preferably without drawing-off.
In above-mentioned technical proposal, the finish of the use that oils described in step (2) is preferably ammonia modified silicon oil, finish it is dense
Degree is preferably 0.1wt%~1wt%；The temperature of the compacting by drying is preferably 60~160 DEG C, more preferably 40~140 DEG C；
The pressure of the steam drafting is preferably 0.1-0.4MPa, and draw ratio is preferably 1~4 times；The thermal finalization is preferably steam heat
Sizing, the pressure of steam thermal finalization is preferably 0.1-0.3MPa.
In above-mentioned technical proposal, the test method of stoste viscosity be using rotational rheometer, shear rate 0.1s-1~
10s-1, test condition include plus shear and be not added with advance pre- two kinds of shearing；The test method of stoste viscosity average molecular weigh is using black formula
Viscosimeter is tested, and test condition is：20 DEG C~60 DEG C of temperature, solvent is using the dimethylformamide of addition electrolyte, electricity
Solve matter and select at least one of lithium bromide or sodium nitrate；The test method of stoste molecular weight distribution (Mw/Mn) is to use high temperature
Gel permeation chromatography is tested；The test condition of stoste molecular weight distribution (Mw/Mn) is：Temperature 50 C~150 DEG C, mobile phase
The dimethylformamide of addition electrolyte is selected, electrolyte selects at least one of lithium bromide or sodium nitrate.
In above-mentioned technical proposal, filament number is tested according to standard GB/T/T 14335-2008, filament strength and
Monofilament modulus is tested according to standard GB/T/T 14337-2008, and precursor density is tested by density gradient instrument.
It is because although itaconic acid is most common common at present that the present invention, which selects itaconic acid aqueous ammonium as comonomer,
Polycondensation monomer, but its hydrophily is bad, if follow-up progress ammonification, inconvenient, technique is difficult to control, difference between batch
Greatly, so to introduce the comonomer itaconate with hydrophilic radical, but itaconate is insoluble in dimethyl sulfoxide, 60 DEG C
When solubility be only 0.2wt%, dissolution velocity is also very slow, limits itaconic acid ammonium as comonomer in dimethyl sulfoxide system
In use, so be primarily used at present in aqueous deposited polymerization, the present invention is first dissolved itaconate using itaconate
In water, then using itaconate aqueous solution as Third monomer add in polymeric kettle, i.e., hydrophilic radical introduced in system,
Solve the problems, such as that itaconate is insoluble in dimethyl sulfoxide again, simultaneously because the dissolubility of itaconate in water is very excellent,
So the water introduced in system is less than 1000ppm, there is no any influence for copolyreaction, the hydrophilic of excellent performance can be obtained
Property spinning solution, few by that can obtain surface grooves after spinning moulding, the good hydrophily carbon fiber of high intensity, compactness is former
Silk.
Scheme using the present invention, obtained polyacrylonitrile carbon fiber precursor, precursor fiber number are 0.6~1.2dtex, monofilament
Intensity is 7~10cN/dtex, and precursor volume density is 1.17~1.19, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated：
Embodiment
【Embodiment 1】
1st, prepared by stoste：By acrylonitrile (AN) of the 98g through distillation, 1.5g itaconic acids (IA), sodium itaconate aqueous solution (by clothing
Health acid sodium 1.5g is dissolved in 1.5g water), 0.6g azodiisobutyronitriles (AIBN), 400g dimethylacetylamides be added to reactor
In, in the case where being protected with nitrogen, reacted under 60 DEG C of steady temperature 20 it is small when, then spinning solution through removed under reduced pressure residual monomer and
After bubble, polyacrylonitrile copolymer spinning solution is obtained.After tested, molecular weight 100870, molecular weight distribution 2.76, viscosity
It is 58PaS at 60 DEG C, the contact angle of co-polymer membrane and water made of this stoste is 42.7 °
2nd, coagulation forming：Spinning solution is after measuring pump-metered, again pass by 3 μm of filterings, after being extruded by spinning head
It is -30% into the 1st coagulating bath, 20 DEG C of coagulation bath temperature, concentration 50%, draw ratio, the 2nd coagulating bath is 40 DEG C, dense
Spend for 40%, draw ratio 100%, the 3rd coagulating bath is 60 DEG C, concentration 30%, draw ratio 105%, obtains nascent fibre
Dimension.
3rd, drawing-off and washing：After as-spun fibre is by 3 solidifications, 3 drawing-off of hot water, 3 hot water drawing temperatures point are carried out
Wei not be 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple is respectively 1.2,1.4 and 2..After 3 hot water drawing-offs, strand carries out 9 water
Wash, by the way of ladder-elevating temperature, 1-3 roads washing temperature is 50 DEG C, and 4-6 roads washing temperature is 60 DEG C, and 7-9 roads washing temperature is
70 DEG C, water rinses are without drawing-off.
4th, oil and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
For 90 DEG C, followed by once oiling, after oiling, the 2nd compacting by drying is carried out, the temperature of compacting by drying is 120 DEG C.
5th, steam drafting：The fiber that step 4 is obtained carries out steam drafting, and the pressure of steam drafting is 0.2Mpa, drawing-off
Than for 2 times.
6th, steam thermal finalization and receipts silk：Silk is received after the fiber that step 5 obtains is carried out steam thermal finalization, obtains high performance carbon
Fiber precursor, the pressure of steam thermal finalization is 0.2Mpa.
The fiber number of gained precursor is 1.21dtex, and filament strength 8cN/dtex, precursor density is 1.178.
【Embodiment 2】
1st, prepared by stoste：Acrylonitrile (AN) of the 121g through distillation, 1.25g itaconic acids (IA), itaconic acid aqueous solutions of potassium (are incited somebody to action
Itaconic acid potassium 1.5g is dissolved in 1.5g water), 0.75g azodiisobutyronitriles (AIBN), 376gN, dinethylformamide add
Into reactor, under helium protection, when reaction 24 is small under 60 DEG C of steady temperature, then spinning solution is remaining through removed under reduced pressure
After monomer and bubble, polyacrylonitrile copolymer spinning solution is obtained.After tested, molecular weight 145067, molecular weight distribution are
2.61, viscosity is 87PaS at 60 DEG C, and the contact angle of co-polymer membrane and water made of this stoste is 52.5 °.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength 8.3cN/dtex, precursor density is 1.181.
【Embodiment 3】
1st, prepared by stoste：By acrylonitrile (AN) of the 146g through distillation, 2g itaconic acids (IA), itaconic acid aqueous ammonium (by clothing
Health acid ammonium 3g is dissolved in 5g water), 0.9g azodiisobutyronitriles (AIBN) and 350gN, N- dimethylacetylamide be added to reaction
In device, under argon gas protection, reacted under 60 DEG C of steady temperature 26 it is small when, then spinning solution through removed under reduced pressure residual monomer and
After bubble, polyacrylonitrile copolymer spinning solution is obtained.After tested, molecular weight 152560, molecular weight distribution 2.91, viscosity
It is 92PaS at 60 DEG C, the contact angle of co-polymer membrane and water made of this stoste is 45.6 °
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength 8.1cN/dtex, precursor density is 1.183.
【Embodiment 4】
1st, prepared by stoste：By acrylonitrile (AN) of the 120g through distillation, 3g itaconic acids (IA), sodium itaconate aqueous solution (by clothing
Health acid sodium 2g is dissolved in 4g water), 0.5g azodiisobutyronitriles (AIBN) and 375g dimethyl sulfoxide (DMSO)s (DMSO) be added to reaction
In device, under nitrogen protection, reacted under 50 DEG C of steady temperature 28 it is small when, then spinning solution through removed under reduced pressure residual monomer and
After bubble, new acrylonitrile copolymer spinning solution is obtained.After tested, molecular weight 148567, molecular weight distribution 2.74,
Viscosity is 77PaS at 60 DEG C, and the contact angle of co-polymer membrane and water made of this stoste is 50.1 °
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength 9.3cN/dtex, precursor density is 1.185.
【Embodiment 5】
1st, prepared by stoste：By acrylonitrile (AN) of the 120g through distillation, 4g itaconic acids (IA), itaconic acid aqueous solutions of potassium (by clothing
Health acid potassium 1g is dissolved in 3g water), 0.5g azodiisobutyronitriles (AIBN), 375gN, dinethylformamide is added to reactor
In, under nitrogen protection, when reaction 32 is small under 60 DEG C of steady temperature, then spinning solution is gentle through removed under reduced pressure residual monomer
After bubble, new acrylonitrile copolymer spinning solution is obtained.After tested, molecular weight 140567, molecular weight distribution 2.76, glues
Degree is 62PaS at 60 DEG C, and the contact angle of co-polymer membrane and water made of this stoste is 54.6 °.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength 9.9cN/dtex, precursor density is 1.171.
【Embodiment 6】
1st, prepared by stoste：According to the stoste preparation process of embodiment 1.
2nd, coagulation forming：Spinning solution is after measuring pump-metered, again pass by 3 μm of filterings, after being extruded by spinning head
It is -40% into the 1st coagulating bath, 30 DEG C of coagulation bath temperature, concentration 60%, draw ratio, the 2nd coagulating bath is 50 DEG C, dense
Spend for 30%, draw ratio 100%, the 3rd coagulating bath is 60 DEG C, concentration 20%, draw ratio 105%, obtains nascent fibre
Dimension.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength 7.9cN/dtex, precursor density is 1.176.
【Embodiment 7】
1st, prepared by stoste：According to the stoste preparation process of embodiment 1.
2nd, coagulation forming：Spinning solution is after measuring pump-metered, again pass by 3 μm of filterings, after being extruded by spinning head
It is -50% into the 1st coagulating bath, 40 DEG C of coagulation bath temperature, concentration 65%, draw ratio, the 2nd coagulating bath is 60 DEG C, dense
Spend for 30%, draw ratio 100%, the 3rd coagulating bath is 60 DEG C, concentration 20%, draw ratio 115%, the 4th coagulating bath
For 70 DEG C, concentration 20%, draw ratio 150%, obtains as-spun fibre.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 1.15dtex, and filament strength 7.1cN/dtex, precursor density is 1.176.
【Embodiment 8】
1st, prepared by stoste：According to the stoste preparation process of embodiment 1.
2nd, coagulation forming：Spinning solution is after measuring pump-metered, again pass by 3 μm of filterings, after being extruded by spinning head
It is -30% into the 1st coagulating bath, 50 DEG C of coagulation bath temperature, concentration 65%, draw ratio, the 2nd coagulating bath is 60 DEG C, dense
Spend for 20%, draw ratio 100%, the 3rd coagulating bath is 70 DEG C, concentration 10%, draw ratio 120%, obtains nascent fibre
Dimension.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 1.05dtex, and filament strength 8.1cN/dtex, precursor density is 1.178.
【Embodiment 9】
1st, prepared by stoste：According to the stoste preparation process of embodiment 1.
2nd, coagulation forming：Spinning solution is after measuring pump-metered, again pass by 3 μm of filterings, after being extruded by spinning head
It is -35% into the 1st coagulating bath, 60 DEG C of coagulation bath temperature, concentration 75%, draw ratio, the 2nd coagulating bath is 70 DEG C, dense
Spend for 30%, draw ratio 110%, the 3rd coagulating bath is 70 DEG C, concentration 10%, draw ratio 120%, obtains nascent fibre
Dimension.
3rd, drawing-off and washing：After as-spun fibre is by 3 solidifications, 3 drawing-off of hot water, 3 hot water drawing temperatures point are carried out
Wei not be 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple is respectively 1.2,1.2 and 1.2.After 3 hot water drawing-offs, strand carries out 9
Washing, by the way of ladder-elevating temperature, 1-3 roads washing temperature is 50 DEG C, and 4-6 roads washing temperature is 60 DEG C, 7-9 roads washing temperature
For 70 DEG C, water rinses are without drawing-off.
4th, oil and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
For 90 DEG C, followed by once oiling, after oiling, the 2nd compacting by drying is carried out, the temperature of compacting by drying is 120 DEG C.
5th, steam drafting：The fiber that step 4 is obtained carries out steam drafting, and the pressure of steam drafting is 0.15Mpa, drawing-off
Than for 1.6 times.
6th, steam thermal finalization and receipts silk：Silk is received after the fiber that step 5 obtains is carried out steam thermal finalization, obtains high performance carbon
Fiber precursor, the pressure of steam thermal finalization is 0.2Mpa.
The fiber number of gained precursor is 1.21dtex, and filament strength 8.5cN/dtex, precursor density is 1.178.
【Embodiment 10】
1st, prepared by stoste：According to the stoste preparation process of embodiment 1.
2nd, coagulation forming：Spinning solution is after measuring pump-metered, again pass by 3 μm of filterings, after being extruded by spinning head
It is -35% into the 1st coagulating bath, 60 DEG C of coagulation bath temperature, concentration 75%, draw ratio, the 2nd coagulating bath is 70 DEG C, dense
Spend for 30%, draw ratio 110%, the 3rd coagulating bath is 70 DEG C, concentration 10%, draw ratio 120%, obtains nascent fibre
Dimension.
3rd, drawing-off and washing：After as-spun fibre is by 3 solidifications, 3 drawing-off of hot water, 3 hot water drawing temperatures point are carried out
Wei not be 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple is respectively 1.4,1.6 and 1.8.After 3 hot water drawing-offs, strand carries out 9
Washing, by the way of ladder-elevating temperature, 1-4 roads washing temperature is 50 DEG C, and 5-8 roads washing temperature is 60 DEG C, 9-12 roads washing temperature
Spend for 70 DEG C, water rinses are without drawing-off.
4th, oil and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
For 80 DEG C, followed by once oiling, after oiling, the 2nd compacting by drying is carried out, the temperature of compacting by drying is 140 DEG C.
5th, steam drafting：The fiber that step 4 is obtained carries out steam drafting, and the pressure of steam drafting is 0.4Mpa, drawing-off
Than for 3 times.
6th, steam thermal finalization and receipts silk：Silk is received after the fiber that step 5 obtains is carried out steam thermal finalization, obtains high performance carbon
Fiber precursor, the pressure of steam thermal finalization is 0.2Mpa.
The fiber number of gained precursor is 0.75dtex, and filament strength 8.8cN/dtex, precursor density is 1.188.
【Embodiment 11】
1st, prepared by stoste：According to the stoste preparation process of embodiment 1.
2nd, coagulation forming：Spinning solution is after measuring pump-metered, again pass by 3 μm of filterings, after being extruded by spinning head
It is -30% into the 1st coagulating bath, 50 DEG C of coagulation bath temperature, concentration 75%, draw ratio, the 2nd coagulating bath is 50 DEG C, dense
Spend for 30%, draw ratio 105%, the 3rd coagulating bath is 60 DEG C, concentration 15%, draw ratio 110%, obtains nascent fibre
Dimension.
3rd, drawing-off and washing：After as-spun fibre is by 3 solidifications, 3 drawing-off of hot water, 3 hot water drawing temperatures point are carried out
Wei not be 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple is respectively 1.6,2 and 1.8.After 3 hot water drawing-offs, strand carries out 9 water
Wash, by the way of ladder-elevating temperature, 1-4 roads washing temperature is 50 DEG C, and 5-8 roads washing temperature is 60 DEG C, 9-12 roads washing temperature
For 70 DEG C, water rinses are without drawing-off.
4th, oil and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
For 85 DEG C, followed by once oiling, after oiling, the 2nd compacting by drying is carried out, the temperature of compacting by drying is 155 DEG C.
5th, steam drafting：The fiber that step 4 is obtained carries out steam drafting, and the pressure of steam drafting is 0.4Mpa, drawing-off
Than for 2.5 times.
6th, steam thermal finalization and receipts silk：Silk is received after the fiber that step 5 obtains is carried out steam thermal finalization, obtains high performance carbon
Fiber precursor, the pressure of steam thermal finalization is 0.2Mpa.
The fiber number of gained precursor is 0.75dtex, and filament strength 10cN/dtex, precursor density is 1.188.
【Embodiment 12】
1st, prepared by stoste：According to the stoste preparation process of embodiment 1.
2nd, coagulation forming：Spinning solution is after measuring pump-metered, again pass by 3 μm of filterings, after being extruded by spinning head
It is -30% into the 1st coagulating bath, 50 DEG C of coagulation bath temperature, concentration 75%, draw ratio, the 2nd coagulating bath is 50 DEG C, dense
Spend for 30%, draw ratio 105%, the 3rd coagulating bath is 60 DEG C, concentration 15%, draw ratio 110%, obtains nascent fibre
Dimension.
3rd, drawing-off and washing：After as-spun fibre is by 3 solidifications, 3 drawing-off of hot water, 3 hot water drawing temperatures point are carried out
Wei not be 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple is respectively 1.8,1.8 and 2.After 3 hot water drawing-offs, strand carries out 9 water
Wash, by the way of ladder-elevating temperature, 1-3 roads washing temperature is 50 DEG C, and 4-6 roads washing temperature is 60 DEG C, and 7-9 roads washing temperature is
70 DEG C, water rinses are without drawing-off.
4th, oil and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
For 85 DEG C, followed by once oiling, after oiling, the 2nd compacting by drying is carried out, the temperature of compacting by drying is 155 DEG C.
5th, steam drafting：The fiber that step 4 is obtained carries out steam drafting, and the pressure of steam drafting is 0.4Mpa, drawing-off
Than for 2 times.
6th, steam thermal finalization and receipts silk：Silk is received after the fiber that step 5 obtains is carried out steam thermal finalization, obtains high performance carbon
Fiber precursor, the pressure of steam thermal finalization is 0.2Mpa.
The fiber number of gained precursor is 0.75dtex, and filament strength 7cN/dtex, precursor density is 1.185.
【Comparative example 1】
1st, prepared by stoste：Acrylonitrile (AN) of the 98g through distillation, 1.5g itaconic acids (IA), sodium itaconate 1.5g, 0.6g is even
Nitrogen bis-isobutyronitrile (AIBN), 400g dimethylacetylamides are added in reactor, since sodium itaconate is in dimethyl sulfoxide (DMSO)
Solubility is too low, so there is part sodium itaconate not to be completely dissolved, causes spinning solution uneven.
【Comparative example 2】
1st, prepared by stoste：By acrylonitrile (AN) of the 97g through distillation, 3g itaconic acids (IA), 0.6g azodiisobutyronitriles
(AIBN), 380gN, dinethylformamide are added in reactor, under nitrogen protection, are reacted under 60 DEG C of steady temperature
20 it is small when, then spinning solution obtains new acrylonitrile copolymer spinning solution after removed under reduced pressure residual monomer and bubble.Through
Test, molecular weight 112560, molecular weight distribution 2.70, viscosity are 167PaS at 60 DEG C, are copolymerized made of this stoste
The contact angle of thing film and water is 58.1 °
2nd, coagulation forming：Spinning solution is after measuring pump-metered, again pass by 3 μm of filterings, after being extruded by spinning head
It is -30% into the 1st coagulating bath, 60 DEG C of coagulation bath temperature, concentration 75%, draw ratio, the 2nd coagulating bath is 60 DEG C, dense
Spend for 30%, draw ratio 105%, the 3rd coagulating bath is 60 DEG C, concentration 15%, draw ratio 110%, obtains nascent fibre
Dimension.
3rd, drawing-off and washing：After as-spun fibre is by 3 solidifications, 3 drawing-off of hot water, 3 hot water drawing temperatures point are carried out
Wei not be 70 DEG C, 80 DEG C and 90 DEG C, drafting multiple is respectively 1.6,1.6 and 1.8.After 3 hot water drawing-offs, strand carries out 9
Washing, by the way of ladder-elevating temperature, 1-3 roads washing temperature is 50 DEG C, and 4-6 roads washing temperature is 60 DEG C, 7-9 roads washing temperature
For 70 DEG C, water rinses are without drawing-off.
4th, oil and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
For 85 DEG C, followed by once oiling, after oiling, the 2nd compacting by drying is carried out, the temperature of compacting by drying is 125 DEG C.
5th, steam drafting：The fiber that step 4 is obtained carries out steam drafting, and the pressure of steam drafting is 0.4Mpa, drawing-off
Than for 2 times.
6th, steam thermal finalization and receipts silk：Silk is received after the fiber that step 5 obtains is carried out steam thermal finalization, obtains high performance carbon
Fiber precursor, the pressure of steam thermal finalization is 0.2Mpa.
Obtained fiber surface groove is serious, and compact structure is poor, and the fiber number of gained precursor is 1.21dtex, and monofilament is strong
It is 1.173 to spend for 5.3cN/dtex, precursor density.
Claims (9)
1. a kind of preparation method of hydrophilic polypropylene itrile group carbon fibre precursor, comprises the following steps：
(1) prepared by stoste：Polymer raw copolymerization component, initiator are mixed with solvent, aggregated reaction obtains spinning solution I,
Spinning solution I is through removed under reduced pressure residual monomer and bubble, the polyacrylonitrile copolymer spinning solution that high-hydrophilic is obtained by filtration；
(2) by the polyacrylonitrile copolymer spinning solution by spinneret extrusion, coagulation forming, washing, drawing-off, oil, do
Silk is received after dry densification, steam drafting, steam thermal finalization and obtains polyacrylonitrile base carbon fiber precursors；
Wherein, the copolymerization component includes acrylonitrile, the first comonomer and the second comonomer；
First comonomer is selected from least one of sodium itaconate, itaconic acid potassium, itaconic acid ammonium；And first copolymerization
Monomer is added in the form of its aqueous solution, and the mass ratio of the first comonomer and water is 1:(0.1~5)；
Second comonomer is acrylamide, acryloyl amidoxime, hydroxylethyl nitrile, α chloroacrylonitriles, diacetone acrylamide
Acid amides, itaconic acid, β-itaconic acid n-butyl, acrylic acid, methyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl
At least one of base acrylic acid；
In prepared by the stoste, the proportioning of polymer raw is counted in parts by weight, and the acrylonitrile is 13~33 parts, and the first copolymerization is single
Body is 1~4 part, and the second comonomer is 1~4 part, and solvent is 65~84 parts, and initiator amount is copolymerization component gross weight
0.2~1%.
2. the preparation method of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that described
The reaction temperature of polymerisation is 30~80 DEG C, it is de- single using vacuum take off it is single by the way of.
3. the preparation method of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 2, it is characterised in that described
The reaction temperature of polymerisation is 40~70 DEG C.
4. the preparation method of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that described
Coagulation forming is using multistage solidification mode, and through twice above coagulating bath, coagulating bath medium is the aqueous solution of dimethyl sulfoxide (DMSO), is solidified
The concentration of bath is solidified using ladder concentration, concentration 10%-80%, and the concentration of first road coagulating bath is dense no more than follow-up coagulating bath
Degree, the temperature of coagulating bath are controlled as 20~70 DEG C, and first road coagulating bath is negative drawing-off, and draw ratio is -5%~-50%, follow-up solidifying
Solid draw ratio be 1~3.
5. the preparation method 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, and per pass carries out drawing-off using 60~90 DEG C of hot water, and hot water draw ratio is controlled at 1~3 times.
6. the preparation method of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that described
Wash and washed for multiple tracks, per pass is washed using 40~80 DEG C, by the way of ladder-elevating temperature, after first road washing temperature is not more than
Continuous washing temperature, water rinses are without drawing-off.
7. the preparation method of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that described
The finish used oil as ammonia modified silicon oil, the concentration of finish is 0.1wt%~1wt%；The temperature of the compacting by drying is
60~160 DEG C.
8. the preparation method of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 7, it is characterised in that：
The temperature of the compacting by drying is 40~140 DEG C.
9. the preparation method of hydrophilic polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that steam
The pressure of drawing-off is 0.1-0.4MPa, and draw ratio is 1~4 times.
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