CN105525378B - The preparation method of high modulus polypropylene itrile group carbon fibre precursor - Google Patents
The preparation method of high modulus polypropylene itrile group carbon fibre precursor Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of high modulus polypropylene itrile group carbon fibre precursor, mainly solve the problem of spinning solution molecular weight existing in the prior art and the smaller requirement that cannot be satisfied high drafting of viscosity.The present invention passes through a kind of preparation method of polyacrylonitrile base carbon fiber precursors, by first part's solvent, copolymerization component, after first part's initiator mixing, under the gas shield inert with reactive material, it polymerize 4 hours 10 minutes at 30 50 DEG C, then add second part solvent and second part initiator, it polymerize 20 30 hours at 50 70 DEG C, stoste is after removed under reduced pressure residual monomer and bubble, by high-performance polyacrylonitrile copolymer spinning solution is obtained by filtration, through solidification, drawing-off, washing, it oils, compacting by drying, silk is received after steam drafting and thermal finalization, the technical solution for obtaining the carbon fibre precursor of high-modulus preferably resolves the problem, it can be used in the industrial production of carbon fibre precursor.
Description
Technical field
The present invention relates to a kind of preparation methods of high modulus 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 Wesy precursor should have heat resistance is high, hole constructs less, few surface defects, compact structure, draftability are good etc.
Feature.
Precursor is the premise for producing high-performance carbon fibre.And high performance precursor then needs to have following feature：(1)
Spinning solution high concentration, spinning solution solid content are higher than 20%, the stoste of the high solids content coagulator water in process of setting
Diffusion velocity it is slack-off, the high precursor of the solidification strand and density that are easy to be made fine and close.(2) molecular weight height, narrow molecular weight distribution
Spinning solution high strength fibre can be made, molecular weight is bigger, and molecule chain end number is fewer, under causing the probability of defect significantly
Drop.But the stoste of high concentration and high molecular weight, dope viscosity can be caused excessively high, gelatin phenomenon is serious, causes spinning tired
It is difficult.
High solids content, high molecular weight spinning solution can ensure PAN precursor important method with high performance, stoste point
Son amount and viscosity are not high enough, can not bear the drawing-off of follow-up high power, the carbon fibre precursor of high-modulus can not be made.It is different with azo two
Heptonitrile reacts to obtain initiator as Acrylamide polymerization, and it is bad to can effectively avoid the side reactions such as oxidation, branched and crosslinking etc.
The generation of structure.
Guo Cong acute hearing et al. (tec fiber with application, 2011,36 (1)) is by the PAN copolymer of common relative molecular mass
It is stirred with the PAN copolymer and DMSO of high relative molecular mass, the high relative molecular mass that mass fraction is 1% is made
PAN copolymer, to improve the performance of spinning solution, to be suitable for rear road dry-jet wet-spinning super drawing, but super high molecular weight
Polyacrylonitrile not readily dissolves, and super-high molecular weight polyacrylonitrile will produce gel in dissolving, so super high molecular weight is poly-
Acrylonitrile can only control in the range of a very little, be less than 1%.
Invention content
When the technical problem to be solved by the present invention is to prepare acrylonitrile copolymer using one-step method in conventional art, general point
The polyacrylonitrile matrix of son amount, dope viscosity is smaller, and the requirement of high drafting when cannot be satisfied spinning cannot be satisfied dry spray
The requirement of wet spinning process；The polyacrylonitrile matrix of super high molecular weight, viscosity is excessive, filtration difficulty, and spinning is unstable；Two-step method system
When for containing super-high molecular weight polyacrylonitrile spinning solution, course of dissolution is not easy to control, easy tos produce gel, and super high molecular weight
The problem of component can only control to a very small extent provides a kind of polymolecular amount composition polyacrylonitrile spinning solution, the original
Liquid is polymerize by solution one-step method, and containing super high molecular weight copolymerization component and conventional molecular weight copolymerization component, having can be suitable for
High drafting, and the stoste viscosity for being suitble to spinning is kept, it is former so as to obtain high compactness, high intensity, high modulus carbon fiber
The advantages of silk.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of high modulus polypropylene itrile group carbon fiber
The preparation method for tieing up precursor, includes the following steps：
(1) prepared by stoste：After first part's solvent, copolymerization component, first part initiator are mixed, with reactive material
Under inert gas shield, it polymerize -4 hours 10 minutes at 30-50 DEG C, then adds second part solvent and second part
Initiator polymerize 20-30 hours at 50-70 DEG C, and stoste is through taking off list, deaeration, high-performance polyacrylonitrile copolymer being obtained by filtration
Spinning solution；
(2) spinning solution through spinneret extrusion, coagulation forming, washing, drawing-off, oil, compacting by drying, steam drafting,
Silk is received after thermal finalization obtains polyacrylonitrile base carbon fiber precursors；
Wherein, the copolymerization component includes acrylonitrile, the first comonomer, the second comonomer；In terms of parts by weight, the
The amount x of a part of solvent and amount y of second part solvent meets relational expression (I, the amount m and second part of first part's initiator
The amount n of initiator meets relational expression (II)：
0≤x/ (x+y) ＜ 1, (I)；
0 ＜ m/ (m+n)≤1, (II)；
Wherein, x+y is solvent total amount, and m+n is initiator total amount.
In above-mentioned technical proposal, the high-performance polyacrylonitrile copolymer spinning solution includes viscosity average molecular weigh 500,000-300
Ten thousand, the super high molecular weight acrylonitrile copolymer of molecular weight distribution 1-5, dope viscosity are 100-300Pas at 50 DEG C.
In above-mentioned technical proposal, in terms of parts by weight, first part's solvent preferably accounts for the 0.1~89.9% of solvent total amount,
Second part solvent is surplus；First part's initiator preferably accounts for initiator total amount 1-99%, and second part initiator is surplus.
In above-mentioned technical proposal, first monomer and second comonomer can be selected from well-known to those skilled in the art
Any one in comonomer, can achieve the object of the present invention；Such as but do not limit the first monomer preferably be selected from formula (I),
At least one of structure shown in formula (II)：
Wherein, R1、R2、R3、R4It is independently chosen from H or C1~C4Alkyl；Such as be selected from formula (I) has itaconic acid, β-clothing health
Acid butyl ester etc. has acrylic acid, methyl acrylate, methyl methacrylate, ethyl methacrylate etc. selected from formula (II)；First
Monomer is more preferably at least one of itaconic acid, methyl acrylate, methyl methacrylate.Such as but do not limit second
Monomer preferably is selected from isobutyl group acrylic acid, acrylamide, acryloyl amidoxime, hydroxylethyl nitrile, α chloroacrylonitriles or diacetone third
At least one of acrylamide；Second comonomer is more preferably at least one of acrylamide, acryloyl amidoxime.
In above-mentioned technical proposal：The proportioning of polymer raw is counted in parts by weight in prepared by the stoste, and the acrylonitrile is excellent
7~33 parts are selected as, first comonomer is preferably 1~4 part, and second comonomer is preferably 1~4 part, described molten
Agent is preferably 65~85 parts, and the initiator is preferably the 0.2~1% of copolymerization component total weight, and initiator can be this field
Common various types of initiators known to technical staff, such as but be not limited to azo compound (such as azo two is different
Butyronitrile, azobisisovaleronitrile, azobisisoheptonitrile etc.)；Described take off singly refers to removing residual monomer, and art technology may be used
Conventional processing technique known to personnel, it is preferred to use vacuum takes off single mode；The deaeration refers in removing polymerization stoste
Bubble can also use conventional technical means, such as vacuum mode；The filter type is preferably Multi-channel filtering, more preferably
More than twice to filter, per pass filtering accuracy is preferably independently 1-5 μm, and filter screen material is preferably sintered metal net or sintering
Metal felt.
In above-mentioned technical proposal, the initiator is further preferably from azodiisobutyronitrile, azobisisovaleronitrile and azo
At least one of two different heptonitriles are two or more；The gas inert to reactive material is selected from nitrogen, argon gas or helium
At least one of.
In above-mentioned technical proposal, this may be used in the polyacrylonitrile base carbon fiber precursors spinning technique in the step (2)
Field technology personnel the ripe common process, such as wet spinning, dry-jet wet-spinning of the prior art 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.
In above-mentioned technical proposal, the coagulation forming preferably uses 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 preferably uses ladder concentration to solidify, and concentration is excellent
It is selected as 10%-80%, 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, the preferably negative drawing-off of first road coagulating bath, draw ratio is preferably -5%~-50%, and the draw ratio subsequently solidified is excellent
It is selected as 1~3.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 uses 60~90 DEG C of hot water to carry out drawing-off, and hot water draw ratio is both preferably 1~4 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 preferably uses 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 solvent can be it is well-known to those skilled in the art any one or it is two or more
Mixture, such as but do not limit dimethyl sulfoxide (DMSO), n,N-Dimethylformamide, n,N-dimethylacetamide；First part is molten
Agent and second part solvent can be identical can also be different.
In above-mentioned technical proposal, first part's initiator and second part initiator preferably independently are selected from azo
Close object；First part's initiator is more preferably different from second part initiator.
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 adding to shear and be not added in 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
It solves matter and selects 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, electrolyte is selected to select at least one of lithium bromide or sodium nitrate.
In above-mentioned technical proposal, GB/T 14335-2008 are tested filament number according to national standards, filament strength and
GB/T 14337-2008 are tested monofilament modulus according to national standards, and precursor density is tested by density gradient instrument.
Due to the method using the substep addition of different initiators in the present invention, can be obtained by one-step method polymerisation in solution more
Molecular weight forms polyacrylonitrile spinning solution.Super high molecular weight copolymerization component is prepared first, then by introducing solvent and drawing
Hair agent obtains the copolymerization component of conventional molecular weight so that stoste can meet the requirement of high drafting, while can be with control system
Viscosity to keep the stability of spinning, and can change stoste by adjusting super high molecular weight copolymerization component content
Performance requires to meet the different of subsequent handling.
Scheme using the present invention, obtained high modulus polypropylene nitrile carbon fibre precursor, precursor fiber number be 0.6~
1.2dtex, filament strength be 7~10cN/dtex, monofilament modulus be 115~130cN/dtex, precursor volume density be 1.17~
1.19, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated：
Specific implementation mode
【Embodiment 1】
1, prepared by stoste：By acrylonitrile (AN) 90g, methyl methacrylate 5g, isobutyl group acrylic acid 5g, N through distillation,
Dinethylformamide 100g, azobisisoheptonitrile (ABVN) 0.001g are added in reactor, under nitrogen protection, at 30 DEG C
Steady temperature under react 1 hour, then proceed to that n,N-Dimethylformamide 300g and azodiisobutyronitrile (AIBN) is added
0.5g, reacts 20 hours under 60 DEG C of steady temperature, and then spinning solution is contained after removed under reduced pressure residual monomer and bubble
There is super high molecular weight acrylonitrile copolymer spinning solution, then spinning solution is after removed under reduced pressure residual monomer and bubble, by 5 μm
The filtering of filtering material obtains polymolecular amount composition polyacrylonitrile spinning solution.After tested, containing super high molecular weight copolymerization component
Viscosity average molecular weigh be 4,850,000, molecular weight distribution 2.34, polyacrylonitrile spinning solution viscosity at 50 DEG C be 487PaS.
2, coagulation forming：Spinning solution is after measuring pump-metered, again passing by 3 μm of filterings, after being squeezed out by spinning head
Into the 1st coagulating bath, 20 DEG C of coagulation bath temperature, a concentration of 50%, draw ratio is -30%, and the 2nd coagulating bath is 40 DEG C, dense
Degree is 40%, draw ratio 110%, and the 3rd coagulating bath is 60 DEG C, a concentration of 30%, draw ratio 110% obtains nascent fibre
Dimension.
3, 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 2,2 and 2..After 3 hot water drawing-offs, strand carries out 9 washings,
By the way of ladder-elevating temperature, the roads 1-3 washing temperature is 50 DEG C, and the roads 4-6 washing temperature is 60 DEG C, and the roads 7-9 washing temperature is 70
DEG C, water rinses are without drawing-off.
4, it oils and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
It is 90 DEG C, followed by once oiling, after oiling, carries out the 2nd compacting by drying, the temperature of compacting by drying is 120 DEG C.
5, 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 being 5 times.
6, 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
The pressure of fiber precursor, steam thermal finalization is 0.2Mpa.
The fiber number of gained precursor is 0.7dtex, and filament strength 9.5cN/dtex, precursor modulus is 130cN/dtex, former
Silk density is 1.178.
【Embodiment 2】
1, prepared by stoste：By acrylonitrile (AN) 92g, itaconic acid 2g, acrylamide 6g, N through distillation, N- dimethyl formyls
Amine 150g, azobisisoheptonitrile (ABVN) 0.01g are added in reactor, under nitrogen protection, under 40 DEG C of steady temperature
Reaction 2 hours then proceedes to that n,N-Dimethylformamide 300g and azodiisobutyronitrile (AIBN) 0.8g is added, in 50 DEG C of perseverance
Determine to react 24 hours at temperature, then spinning solution obtains after removed under reduced pressure residual monomer and bubble containing super high molecular weight third
Alkene lonitrile copolymer spinning solution.After tested, the viscosity average molecular weigh containing super high molecular weight copolymerization component is 4,590,000, molecular weight point
Cloth is 3.49, and polyacrylonitrile spinning solution viscosity is 455PaS at 50 DEG C.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.73dtex, and filament strength 8.8cN/dtex, precursor modulus is 125cN/dtex, former
Silk density is 1.181.
【Embodiment 3】
1, prepared by stoste：By acrylonitrile (AN) 93g, β-itaconic acid n-butyl 3.5g, acryloyl amidoxime 3.5g, N through distillation,
N- dimethylacetylamides 186g, azobisisoheptonitrile (ABVN) 0.1g are added in reactor, under nitrogen protection, at 50 DEG C
It is reacted 3 hours under steady temperature, then proceedes to that n,N-Dimethylformamide 100g and azodiisobutyronitrile (AIBN) 0.6g is added,
React 22 hours under 55 DEG C of steady temperature, then spinning solution obtains after removed under reduced pressure residual monomer and bubble containing super
High-molecular weight vinyl cyanide copolymer spinning solution.Then spinning solution filters after removed under reduced pressure residual monomer and bubble by 5 μm
The filtering of material obtains high-performance polyacrylonitrile copolymer spinning solution.After tested, viscous containing super high molecular weight copolymerization component
Average molecular weight is 3,000,000, molecular weight distribution 4.97, and the viscosity average molecular weigh of copolymerization component B is 130,000, and molecular weight distribution is
5.66, polyacrylonitrile spinning solution viscosity is 409PaS at 50 DEG C.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.73dtex, and filament strength 9.5cN/dtex, precursor modulus is 128cN/dtex, former
Silk density is 1.183.
【Embodiment 4】
1, prepared by stoste：By through distillation acrylonitrile (AN) 94g, methyl methacrylate 2g, hydroxylethyl nitrile 3g, two
Methyl sulfoxide 100g, azobisisoheptonitrile (ABVN) 0.01g are added in reactor, under nitrogen protection, constant at 30 DEG C
At a temperature of react 4 hours, then proceed to be added dimethyl sulfoxide (DMSO) 200g and azodiisobutyronitrile (AIBN) 0.5g, in 60 DEG C of perseverance
Determine to react 20 hours at temperature, then spinning solution obtains after removed under reduced pressure residual monomer and bubble containing super high molecular weight third
Then spinning solution is after removed under reduced pressure residual monomer and bubble for alkene lonitrile copolymer spinning solution, by the filtering of 5 μm of filtering materials,
Obtain high-performance polyacrylonitrile copolymer spinning solution.After tested, the viscosity average molecular weigh containing super high molecular weight copolymerization component is
2780000, molecular weight distribution 2.34, polyacrylonitrile spinning solution viscosity is 368PaS at 50 DEG C.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.72dtex, and filament strength 8.8cN/dtex, precursor density is 1.185.
【Embodiment 5】
1, prepared by stoste：By acrylonitrile (AN) 95g, ethyl methacrylate 3g, α chloroacrylonitrile 2g, N through distillation,
Dinethylformamide 200g, azobisisoheptonitrile (ABVN) 0.1g are added in reactor, under nitrogen protection, at 30 DEG C
It is reacted 30 minutes under steady temperature, then proceedes to that n,N-Dimethylformamide 300g and azodiisobutyronitrile (AIBN) is added
0.5g, reacts 20 hours under 60 DEG C of steady temperature, and then spinning solution is contained after removed under reduced pressure residual monomer and bubble
There is super high molecular weight acrylonitrile copolymer spinning solution.Then spinning solution is after removed under reduced pressure residual monomer and bubble, by 5 μm
The filtering of filtering material obtains high-performance polyacrylonitrile copolymer spinning solution.After tested, containing super high molecular weight copolymerization component
Viscosity average molecular weigh be 2,050,000, molecular weight distribution 2.34, polyacrylonitrile spinning solution viscosity at 50 DEG C be 346PaS.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.76dtex, and filament strength 8.3cN/dtex, precursor modulus is 118cN/dtex, former
Silk density is 1.171.
【Embodiment 6】
1, prepared by stoste：According to the stoste preparation process of embodiment 1.
2, coagulation forming：Spinning solution is after measuring pump-metered, again passing by 3 μm of filterings, after being squeezed out by spinning head
Into the 1st coagulating bath, 30 DEG C of coagulation bath temperature, a concentration of 60%, draw ratio is -40%, and the 2nd coagulating bath is 50 DEG C, dense
Degree is 30%, draw ratio 100%, and the 3rd coagulating bath is 60 DEG C, a concentration of 20%, draw ratio 105% obtains nascent fibre
Dimension.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.71dtex, and filament strength 7.9cN/dtex, precursor modulus is 111cN/dtex, former
Silk density is 1.176.
【Embodiment 7】
1, prepared by stoste：According to the stoste preparation process of embodiment 1.
2, coagulation forming：Spinning solution is after measuring pump-metered, again passing by 3 μm of filterings, after being squeezed out by spinning head
Into the 1st coagulating bath, 40 DEG C of coagulation bath temperature, a concentration of 65%, draw ratio is -50%, and the 2nd coagulating bath is 60 DEG C, dense
Degree be 30%, draw ratio 100%, the 3rd coagulating bath be 60 DEG C, a concentration of 20%, draw ratio 115%, the 4th coagulating bath
It is 70 DEG C, a concentration of 20%, draw ratio 150% obtains as-spun fibre.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.71dtex, and filament strength 8.2cN/dtex, precursor modulus is 118cN/dtex, former
Silk density is 1.176.
【Embodiment 8】
1, prepared by stoste：According to the stoste preparation process of embodiment 1.
2, coagulation forming：Spinning solution is after measuring pump-metered, again passing by 3 μm of filterings, after being squeezed out by spinning head
Into the 1st coagulating bath, 50 DEG C of coagulation bath temperature, a concentration of 65%, draw ratio is -30%, and the 2nd coagulating bath is 60 DEG C, dense
Degree is 20%, draw ratio 100%, and the 3rd coagulating bath is 70 DEG C, a concentration of 10%, draw ratio 120% obtains nascent fibre
Dimension.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.68dtex, and filament strength 9.4cN/dtex, precursor modulus is 122cN/dtex, former
Silk density is 1.178.
【Embodiment 9】
1, prepared by stoste：According to the stoste preparation process of embodiment 1.
2, coagulation forming：Spinning solution is after measuring pump-metered, again passing by 3 μm of filterings, after being squeezed out by spinning head
Into the 1st coagulating bath, 60 DEG C of coagulation bath temperature, a concentration of 75%, draw ratio is -35%, and the 2nd coagulating bath is 70 DEG C, dense
Degree is 30%, draw ratio 110%, and the 3rd coagulating bath is 70 DEG C, a concentration of 10%, draw ratio 120% obtains nascent fibre
Dimension.
3, 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, the roads 1-3 washing temperature is 50 DEG C, and the roads 4-6 washing temperature is 60 DEG C, the roads 7-9 washing temperature
It it is 70 DEG C, water rinses are without drawing-off.
4, it oils and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
It is 90 DEG C, followed by once oiling, after oiling, carries out the 2nd compacting by drying, the temperature of compacting by drying is 120 DEG C.
5, 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 being 1.6 times.
6, 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
The pressure of fiber precursor, steam thermal finalization is 0.2Mpa.
The fiber number of gained precursor is 0.6dtex, and filament strength 8.5cN/dtex, precursor modulus is 120cN/dtex, former
Silk density is 1.178.
【Embodiment 10】
1, prepared by stoste：According to the stoste preparation process of embodiment 1.
2, coagulation forming：Spinning solution is after measuring pump-metered, again passing by 3 μm of filterings, after being squeezed out by spinning head
Into the 1st coagulating bath, 60 DEG C of coagulation bath temperature, a concentration of 75%, draw ratio is -35%, and the 2nd coagulating bath is 70 DEG C, dense
Degree is 30%, draw ratio 110%, and the 3rd coagulating bath is 70 DEG C, a concentration of 10%, draw ratio 120% obtains nascent fibre
Dimension.
3, 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, the roads 1-4 washing temperature is 50 DEG C, and the roads 5-8 washing temperature is 60 DEG C, the roads 9-12 washing temperature
Degree is 70 DEG C, and water rinses are without drawing-off.
4, it oils and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
It is 80 DEG C, followed by once oiling, after oiling, carries out the 2nd compacting by drying, the temperature of compacting by drying is 140 DEG C.
5, 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 being 3 times.
6, 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
The pressure of fiber precursor, steam thermal finalization is 0.2Mpa.
The fiber number of gained precursor is 0.75dtex, and filament strength 7.8cN/dtex, precursor density is 1.188.
【Embodiment 11】
1, prepared by stoste：According to the stoste preparation process of embodiment 1.
2, coagulation forming：Spinning solution is after measuring pump-metered, again passing by 3 μm of filterings, after being squeezed out by spinning head
Into the 1st coagulating bath, 50 DEG C of coagulation bath temperature, a concentration of 75%, draw ratio is -30%, and the 2nd coagulating bath is 50 DEG C, dense
Degree is 30%, draw ratio 105%, and the 3rd coagulating bath is 60 DEG C, a concentration of 15%, draw ratio 110% obtains nascent fibre
Dimension.
3, 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
It washes, by the way of ladder-elevating temperature, the roads 1-4 washing temperature is 50 DEG C, and the roads 5-8 washing temperature is 60 DEG C, the roads 9-12 washing temperature
It it is 70 DEG C, water rinses are without drawing-off.
4, it oils and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
It is 85 DEG C, followed by once oiling, after oiling, carries out the 2nd compacting by drying, the temperature of compacting by drying is 155 DEG C.
5, 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 being 2.5 times.
6, 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
The pressure of fiber precursor, steam thermal finalization is 0.2Mpa.
The fiber number of gained precursor is 0.65dtex, and filament strength 8.9cN/dtex, precursor modulus is 127cN/dtex, former
Silk density is 1.188.
【Embodiment 12】
1, prepared by stoste：According to the stoste preparation process of embodiment 1.
2, coagulation forming：Spinning solution is after measuring pump-metered, again passing by 3 μm of filterings, after being squeezed out by spinning head
Into the 1st coagulating bath, 50 DEG C of coagulation bath temperature, a concentration of 75%, draw ratio is -30%, and the 2nd coagulating bath is 50 DEG C, dense
Degree is 30%, draw ratio 105%, and the 3rd coagulating bath is 60 DEG C, a concentration of 15%, draw ratio 110% obtains nascent fibre
Dimension.
3, 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
It washes, by the way of ladder-elevating temperature, the roads 1-3 washing temperature is 50 DEG C, and the roads 4-6 washing temperature is 60 DEG C, and the roads 7-9 washing temperature is
70 DEG C, water rinses are without drawing-off.
4, it oils and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
It is 85 DEG C, followed by once oiling, after oiling, carries out the 2nd compacting by drying, the temperature of compacting by drying is 155 DEG C.
5, 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 being 2 times.
6, 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
The pressure of fiber precursor, steam thermal finalization is 0.2Mpa.
The fiber number of gained precursor is 0.75dtex, and filament strength 7.6cN/dtex, precursor modulus is 125cN/dtex, former
Silk density is 1.185.
【Embodiment 13】
1, prepared by stoste：By acrylonitrile (AN) 90g, methyl methacrylate 5g, isobutyl group acrylic acid 5g, N through distillation,
Dinethylformamide 100g, azobisisoheptonitrile (ABVN) 0.001g are added in reactor, under nitrogen protection, at 30 DEG C
Steady temperature under react 1 hour, then proceed to that n,N-Dimethylformamide 300g and azobisisoheptonitrile (ABVN) is added
0.5g, reacts 20 hours under 60 DEG C of steady temperature, and then spinning solution is contained after removed under reduced pressure residual monomer and bubble
There is super high molecular weight acrylonitrile copolymer spinning solution, then spinning solution is after removed under reduced pressure residual monomer and bubble, by 5 μm
The filtering of filtering material obtains polymolecular amount composition polyacrylonitrile spinning solution.After tested, containing super high molecular weight copolymerization component
Viscosity average molecular weigh be 3,550,000, molecular weight distribution 3.54, polyacrylonitrile spinning solution viscosity at 50 DEG C be 387Pas.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.74dtex, and filament strength 8.9cN/dtex, precursor modulus is 128cN/dtex, former
Silk density is 1.181.
【Embodiment 14】
1, prepared by stoste：By acrylonitrile (AN) 90g, methyl methacrylate 5g, isobutyl group acrylic acid 5g, N through distillation,
Dinethylformamide 100g, azobisisoheptonitrile (ABVN) 0.001g, azodiisobutyronitrile (AIBN) 0.5g are added to reaction
It in device, under nitrogen protection, is reacted 1 hour under 30 DEG C of steady temperature, then proceedes to that n,N-Dimethylformamide is added
300g, reacts 20 hours under 60 DEG C of steady temperature, and then spinning solution is contained after removed under reduced pressure residual monomer and bubble
There is super high molecular weight acrylonitrile copolymer spinning solution, then spinning solution is after removed under reduced pressure residual monomer and bubble, by 5 μm
The filtering of filtering material obtains polymolecular amount composition polyacrylonitrile spinning solution.After tested, containing super high molecular weight copolymerization component
Viscosity average molecular weigh be 2,950,000, molecular weight distribution 2.84, polyacrylonitrile spinning solution viscosity at 50 DEG C be 287Pas.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.75dtex, and filament strength 8.6cN/dtex, precursor modulus is 124cN/dtex, former
Silk density is 1.181.
【Embodiment 15】
1, prepared by stoste：By acrylonitrile (AN) 90g, methyl methacrylate 5g, isobutyl group acrylic acid 5g, N through distillation,
Dinethylformamide 100g, azodiisobutyronitrile (AIBN) 0.501g are added in reactor, under nitrogen protection, at 30 DEG C
Steady temperature under react 1 hour, then proceed to be added n,N-Dimethylformamide 300g, reacted under 60 DEG C of steady temperature
20 hours, then spinning solution after removed under reduced pressure residual monomer and bubble, obtain containing super high molecular weight acrylonitrile copolymer spin
Silk stock solution, then spinning solution, by the filtering of 5 μm of filtering materials, obtain polymolecular after removed under reduced pressure residual monomer and bubble
Amount composition polyacrylonitrile spinning solution.After tested, the viscosity average molecular weigh containing super high molecular weight copolymerization component is 100,000, molecular weight
2.34 are distributed as, polyacrylonitrile spinning solution viscosity is 56Pas at 50 DEG C.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.75dtex, and filament strength 8.6cN/dtex, precursor modulus is 124cN/dtex, former
Silk density is 1.181.
【Embodiment 16】
1, prepared by stoste：By acrylonitrile (AN) 90g, methyl methacrylate 5g, isobutyl group acrylic acid 5g, N through distillation,
Dinethylformamide 400g, azobisisoheptonitrile (ABVN) 0.001g are added in reactor, under nitrogen protection, at 30 DEG C
Steady temperature under react 1 hour, then proceed to that azodiisobutyronitrile (AIBN) 0.5g is added, it is anti-under 60 DEG C of steady temperature
Answer 20 hours, then spinning solution obtains after removed under reduced pressure residual monomer and bubble containing super high molecular weight acrylonitrile copolymer
Spinning solution.After tested, the viscosity average molecular weigh containing super high molecular weight copolymerization component is 100,000, and molecular weight distribution 2.34 is gathered
Acrylonitrile dope viscosity is 56Pas at 50 DEG C.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.75dtex, and filament strength 8.6cN/dtex, precursor modulus is 124cN/dtex, former
Silk density is 1.181.
【Embodiment 17】
1, prepared by stoste：By acrylonitrile (AN) 90g, methyl methacrylate 5g, isobutyl group acrylic acid 5g, N through distillation,
Dinethylformamide 100g, azobisisoheptonitrile (ABVN) 0.001g are added in reactor, under nitrogen protection, at 30 DEG C
Steady temperature under react 1 hour, then proceed to that n,N-Dimethylformamide 300g and azodiisobutyronitrile (AIBN) is added
0.5g, reacts 20 hours under 60 DEG C of steady temperature, and then spinning solution is contained after removed under reduced pressure residual monomer and bubble
There is super high molecular weight acrylonitrile copolymer spinning solution, then spinning solution is after removed under reduced pressure residual monomer and bubble, by 5 μm
The filtering of filtering material obtains polymolecular amount composition polyacrylonitrile spinning solution.After tested, containing super high molecular weight copolymerization component
Viscosity average molecular weigh be 4,850,000, molecular weight distribution 2.34, polyacrylonitrile spinning solution viscosity at 50 DEG C be 487PaS.
Carry out coagulation forming, drawing-off and washing according to common process condition in the prior art, oil and compacting by drying,
Steam drafting, steam thermal finalization and receipts silk obtain high-performance carbon fibre precursor.
The fiber number of gained precursor is 0.73dtex, and filament strength 8.7cN/dtex, precursor modulus is 122cN/dtex, former
Silk density is 1.172.
【Comparative example 1】(it is year-on-year with embodiment 1, it may be closest to art methods：Mixed initiator synchronizes addition, molten
Agent is not added step by step)
1, prepared by stoste：By acrylonitrile (AN) 90g, methyl methacrylate 5g, isobutyl group acrylic acid 5g, N through distillation,
Dinethylformamide 400g, azobisisoheptonitrile (ABVN) 0.001g, azodiisobutyronitrile (AIBN) 0.5g are added to reaction
In device, under nitrogen protection, reacted 1 hour under 30 DEG C of steady temperature, then reacted 20 hours under 60 DEG C of steady temperature,
Then spinning solution obtains after removed under reduced pressure residual monomer and bubble containing super high molecular weight acrylonitrile copolymer spinning solution,
Then spinning solution, by the filtering of 5 μm of filtering materials, it is poly- to obtain polymolecular amount composition after removed under reduced pressure residual monomer and bubble
Acrylonitrile spinning solution.After tested, the viscosity average molecular weigh containing super high molecular weight copolymerization component is 120,000, and molecular weight distribution is
3.34, polyacrylonitrile spinning solution viscosity is 87Pas at 50 DEG C.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.73dtex, and filament strength 4.8cN/dtex, precursor modulus is 115cN/dtex, former
Silk density is 1.171.
【Comparative example 2】(, possible art methods year-on-year with embodiment 1：Single initiator, solvent substep add)
1, prepared by stoste：By acrylonitrile (AN) 90g, methyl methacrylate 5g, isobutyl group acrylic acid 5g, N through distillation,
Dinethylformamide 100g, azodiisobutyronitrile (AIBN) 0.501g are added in reactor, under nitrogen protection, at 30 DEG C
Steady temperature under react 1 hour, then proceed to be added n,N-Dimethylformamide 300g, reacted under 60 DEG C of steady temperature
20 hours, then spinning solution after removed under reduced pressure residual monomer and bubble, obtain containing super high molecular weight acrylonitrile copolymer spin
Silk stock solution, then spinning solution, by the filtering of 5 μm of filtering materials, obtain polymolecular after removed under reduced pressure residual monomer and bubble
Amount composition polyacrylonitrile spinning solution.After tested, the viscosity average molecular weigh containing super high molecular weight copolymerization component is 100,000, molecular weight
2.34 are distributed as, polyacrylonitrile spinning solution viscosity is 56Pas at 50 DEG C.
Remaining step is according to embodiment 1.
The fiber number of gained precursor is 0.73dtex, and filament strength 3.8cN/dtex, precursor modulus is 109cN/dtex, former
Silk density is 1.161.
【Comparative example 3】
1, prepared by stoste：By acrylonitrile (AN) 98g, itaconic acid 1g, acrylamide 1g, dimethyl sulfoxide (DMSO) through distillation
300g, azodiisobutyronitrile (AIBN) 0.6g are added in reactor, under nitrogen protection, are reacted under 60 DEG C of steady temperature
20 hours, obtain polyacrylonitrile spinning solution.After tested, the viscosity average molecular weigh containing super high molecular weight copolymerization component is 150,000,
Molecular weight distribution is 3.54, and polyacrylonitrile spinning solution viscosity is 78PaS at 50 DEG C.Stoste viscosity is very big, and gel is existing
As apparent, after taking off list deaeration, 3 μm of filtering are carried out
2, coagulation forming：Spinning solution by metering pump-metered, again pass by 3 μm filtering after (, after being squeezed out by spinning head
Into the 1st coagulating bath, 60 DEG C of coagulation bath temperature, a concentration of 75%, draw ratio is -30%, and the 2nd coagulating bath is 60 DEG C, dense
Degree is 30%, draw ratio 105%, and the 3rd coagulating bath is 60 DEG C, a concentration of 15%, draw ratio 110% obtains nascent fibre
Dimension.
3, 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 1.6.After 3 hot water drawing-offs, strand carries out 9
Washing, by the way of ladder-elevating temperature, the roads 1-3 washing temperature is 50 DEG C, and the roads 4-6 washing temperature is 60 DEG C, the roads 7-9 washing temperature
It it is 70 DEG C, water rinses are without drawing-off.
4, it oils and compacting by drying：Compacting by drying, temperature are carried out after the fiber progress 1 that step 3 obtains is oiled
It is 85 DEG C, followed by once oiling, after oiling, carries out the 2nd compacting by drying, the temperature of compacting by drying is 125 DEG C.
5, 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 being 1.5 times.
6, 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
The pressure of fiber precursor, steam thermal finalization is 0.2Mpa.
Spinning process is stablized, and the fiber number of gained precursor is 0.8dtex, filament strength 4.5cN/dtex, and precursor density is
1.173, fiber modulus 105cN/dtex.
If precursor carries out the drawing-off of more high magnification numbe, lousiness situation is serious.
【Comparative example 4】
Convenient molecular weight (molecular weight is 130,000) polyacrylonitrile powder 99g, super high molecular weight (molecular weight is 1,000,000) is poly-
Acrylonitrile powder, dimethyl sulfoxide (DMSO) 300g, it is added in the reactor with stirring, under nitrogen protection, in 60 DEG C of steady temperature
It is lower to be first swollen 48 hours, it is stirred for dissolving 24 hours, polyacrylonitrile spinning solution is obtained, in spinning process, 5 μm can not be passed through
The filtering of filtering material, spinning process is unstable, and being stretched by 14 times just has the generation of fracture of wire lousiness, can not bear more high magnification numbe and lead
It stretches.
Claims (10)
1. a kind of preparation method of high modulus polypropylene itrile group carbon fibre precursor, includes the following steps：
(1) prepared by stoste：It is being in lazy with reactive material after first part's solvent, copolymerization component, first part's initiator are mixed
Property gas shield under, polymerize -4 hours 10 minutes at 30-50 DEG C, then add second part solvent and second part and cause
Agent polymerize 20-30 hours at 50-70 DEG C, obtains polymerization stoste；Polymerization stoste is gathered through taking off list, deaeration, high-performance being obtained by filtration
Acrylonitrile copolymer spinning solution；
(2) spinning solution through spinneret extrusion, coagulation forming, washing, drawing-off, oil, compacting by drying, steam drafting, heat it is fixed
Silk is received after type obtains polyacrylonitrile base carbon fiber precursors；
Wherein, the copolymerization component includes acrylonitrile, the first comonomer, the second comonomer；In terms of parts by weight, first
The amount y of the amount x for dividing solvent and second part solvent meets relational expression (I), and amount m and the second part of first part's initiator cause
The amount n of agent meets relational expression (II)：
0≤x/ (x+y) ＜ 1, (I)；
0 ＜ m/ (m+n)≤1, (II)；
Wherein, x+y is solvent total amount, and m+n is initiator total amount；First part's initiator and second part initiator are only
It is vertical to be selected from least one of azodiisobutyronitrile, azobisisovaleronitrile and azobisisoheptonitrile or two or more；And institute
It states first part's initiator and is different from second part initiator.
2. the preparation method of high modulus polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that described
The proportioning of polymer raw is counted in parts by weight in prepared by stoste, and the acrylonitrile is 7~33 parts, and first comonomer is 1
~4 parts, second comonomer is 1~4 part, and the solvent is 65~85 parts, and the initiator is copolymerization component total weight
0.2~1%.
3. the preparation method of high modulus 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 the above coagulating bath of twice, coagulating bath medium is the aqueous solution of dimethyl sulfoxide (DMSO), solidification
The concentration of bath is solidified using ladder concentration, a concentration of 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 is 20~70 DEG C, and first road coagulating bath is negative drawing-off, and draw ratio is -5%~-50%, is subsequently solidified
Draw ratio is 1~3.
4. the preparation method of high modulus polypropylene itrile group carbon fibre precursor according to claim 3, it is characterised in that described
The temperature of coagulating bath a concentration of 20%~70%, coagulating bath is 30~60 DEG C, and first road coagulating bath draw ratio is -20%~-40%.
5. the preparation method of high modulus 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 is all made of 60~90 DEG C of hot water and carries out drawing-off, and hot water draw ratio is controlled at 1~4 times.
6. the preparation method of high modulus polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that described
Washing is that multiple tracks is washed, and per pass is all made of 40~80 DEG C of washings, 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 high modulus 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, a concentration of 0.1wt%~1wt% of finish.
8. the preparation method of high modulus polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that dry
The temperature of densification is 60~160 DEG C.
9. the preparation method of high modulus 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.
10. the preparation method of high modulus polypropylene itrile group carbon fibre precursor according to claim 1, it is characterised in that described
Thermal finalization is steam thermal finalization.
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