CN104562265A - Preparation method of polyacrylonitrile-based carbon fiber precursor - Google Patents
Preparation method of polyacrylonitrile-based carbon fiber precursor Download PDFInfo
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Abstract
The invention relates to a preparation method of a polyacrylonitrile-based carbon fiber precursor, and mainly aims at solving the problems that a carbon fiber spinning solution prepared from azobisisoheptonitrile as an initiator in the prior art is over-large in viscosity, and poor in spinnability, and the carbon fiber precursor obtained by spinning is low in strength and unstable in property. Through the technical scheme, the preparation method of the polyacrylonitrile-based carbon fiber precursor comprises the following steps: by taking azobisisoheptonitrile as an initiator, polymerizing a first monomer acrylonitrile and a second monomer itaconic acid through initation of a solvent dimethyl sulfoxide to obtain the spinning solution; carrying out vacuum removal on residual monomer and bubbles from the spinning solution; filtering to obtain a high-property polyacrylonitrile copolymer spinning solution; and carrying out solidifying, drafting, washing, oiling, compacting by drying, steam drafting and steam heat setting on the spinning solution, and then rolling to obtain the carbon fiber precursor with high compactness and high strength, the problems are relatively well solved, and the method can be applied to industrial production of the carbon fiber precursor.
Description
Technical field
The present invention relates to a kind of preparation method of polyacrylonitrile base carbon fiber precursors.
Background technology
Monomer polymerization, the molecular weight of copolymer of gained is between 10-90 ten thousand, molecular weight distribution less than 2.3 (patent No. 200710056083.6), but the spinning solution molecular weight of this system gained is too large, simultaneously in spinning process, system viscosity is too large, and wayward polymerization process, spinnability compares poor.Conventional spinning solution uses thio-alcohol based on lauryl mercaptan or isopropyl alcohol etc. as the chain-transferring agent of radical polymerization in producing, effectively can regulate the molecular weight of acrylonitrile, but can reduce the conversion ratio of monomer.In addition, mercaptan has strong impulse smell and very strong toxicity, though and isopropyl alcohol does not have penetrating odor, but regulating power is inadequate.Use traditional chain-transferring agent while adjustment molecular weight of copolymer, can cause the decline of molecular weight, molecular weight distribution broadens, and these transfer agents are in spinning solution simultaneously, be unsuitable for removal, can affect the performance of carbon fibre precursor in spinning process.(number of patent application: 200710056083.6).
Summary of the invention
The technical problem to be solved in the present invention is that the carbon fiber spinning primary fluid viscosity adopting 2,2'-Azobis(2,4-dimethylvaleronitrile) to prepare as initator in conventional art is excessive, spinnability is poor, the carbon fibre precursor intensity of spinning gained is low, unstable properties, employ polyacrylonitrile spinning solution molecular weight and molecular weight after chain-transferring agent, molecular weight distribution broadens, the problem of precursor degradation, provide a kind of preparation method of polyacrylonitrile base carbon fiber precursors, this preparation method has maintenance high solids content, molecular weight and molecualr weight distribution is almost constant, dope viscosity is declined, improve the spinnability of stoste, thus can high compactness be obtained, the advantage of high-strength carbon fiber precursor.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of polyacrylonitrile base carbon fiber precursors, comprises the following steps:
(1) stoste preparation: solvent dimethyl sulfoxide (DMSO), the first monomers acrylonitrile, second comonomer itaconic acid and initator 2,2'-Azobis(2,4-dimethylvaleronitrile), conditioning agent polymerization are obtained spinning solution, spinning solution is after removed under reduced pressure residual monomer and bubble, filtration obtains high-performance polyacrylonitrile copolymer spinning solution, high-performance polyacrylonitrile copolymer spinning solution solid content is 15% ~ 25%, molecular weight is 11 ~ 200,000, molecular weight distribution is 1 ~ 2.5, when 60 DEG C, viscosity is 50 ~ 100PaS, and high-performance polyacrylonitrile copolymer spinning solution temperature is 50 ~ 70 DEG C;
Wherein, molecular weight regulator is selected from least one in dimethylacetylamide, DMF, DMA;
(2) coagulation forming: high-performance polyacrylonitrile copolymer spinning solution, after measuring pump metering, again filtering, through multiple tracks coagulating bath after being extruded, obtains as-spun fibre by spinning head;
(3) drawing-off and washing: as-spun fibre is through the drawing-off of multiple tracks hot water and multiple tracks washing;
(4) to oil and compacting by drying: fiber step (3) obtained, carry out oiling and compacting by drying, the temperature of compacting by drying is 60 ~ 160 DEG C;
(5) steam drafting: the fiber that step (4) obtains is carried out steam drafting, the pressure of steam drafting is 0.1-0.3Mpa, and draw ratio is 1 ~ 4 times;
(6) steam heat sizing and receipts silk: receive silk after the fiber that step (5) obtains is carried out steam heat sizing, obtain high-performance carbon fibre precursor, the pressure of steam heat sizing is 0.1-0.3Mpa.
In technique scheme, preferred technical scheme, raw materials used quality proportioning is, 2,2'-Azobis(2,4-dimethylvaleronitrile): the first monomer and second comonomer sum are 0.0040 ~ 0.0080:1, the first monomer and second comonomer sum: gross mass is 0.20 ~ 0.30:1; Acrylonitrile: itaconic acid is 96 ~ 99.9:0.1, conditioning agent: dimethyl sulfoxide (DMSO) is 0.010 ~ 0.10:1; Preferred technical scheme, removes residual monomer (de-single) and adopts vacuum to take off single mode; Filter type is that Multi-channel filtering precision is respectively 2-5 μm; Preferred technical scheme, adopt multistage solidification mode, coagulating bath medium is methyl-sulfoxide/aqueous solution, the concentration of coagulating bath adopts ladder concentration to solidify, concentration preferences is between 10%-80%, and the temperature of coagulating bath all controls at 20 ~ 70 DEG C, and the coagulating bath of first road is negative drawing-off, draw ratio preferable range is the draw ratio preferable range that-5% ~-50%, Hou Ji road solidifies is 1 ~ 3; Coagulating bath concentration is preferably between 20% ~ 70%, the temperature of coagulating bath preferably 30 ~ 60 DEG C, and the coagulating bath of first road is negative drawing-off, and draw ratio is preferably-20% ~-40%; The drawing-off of multiple tracks hot water is that employing 60 ~ 90 DEG C of hot water carry out drawing-off, and hot water draw ratio all controls at 1 ~ 3 times; Multiple tracks washing employing 40 ~ 80 DEG C washing, adopt the mode of ladder-elevating temperature, water rinses does not carry out drawing-off; The finish adopted that oils is ammonia modified silicon oil, and the concentration preferences of finish is 0.1wt% ~ 1wt%; The temperature of compacting by drying is preferably 40 ~ 140 DEG C.
Owing to selecting 2,2'-Azobis(2,4-dimethylvaleronitrile) to be initator in the present invention, reaction is carried out at low temperatures, molecular weight can be obtained suitable high by one-step method, the spinning solution of narrow molecular weight distribution, but system viscosity is too large in the course of the polymerization process to use this initator, be not easy heat radiation, system reaction temperature will be made uneven and produce gel, course of reaction is also wayward, the use of 2,2'-Azobis(2,4-dimethylvaleronitrile) is limited by very large, the present invention selects N simultaneously, dinethylformamide, N, at least one in N-dimethylacetylamide is because their chain transfer constant is larger than the chain transfer constant of methyl-sulfoxide as conditioning agent, they are large for the solubility of polyacrylonitrile simultaneously, so dope viscosity can be made to decline, use 2,2'-Azobis(2,4-dimethylvaleronitrile) just can while raising stoste solid content, maintenance spinning solution narrow molecular weight distribution as initator and conditioning agent simultaneously, effective hierarchy of control viscosity, spinnability is improved, and reduces the generation of gel, stoste is easy to filter, in spinning process, head pressure keeps long-time stable, and spinnerets not easily blocks, the stability of the long-acting maintenance spinning of energy.In polymerization, introduce dimethylacetylamide, N simultaneously, dinethylformamide and N, after N-dimethylacetylamide, in spinning process, dimethylacetylamide, DMF, DMA are easy to be diffused into from fiber in coagulating bath and drawing-off and washing, final to carbon fibre precursor in can not remain this type of conditioning agent, the carbon fibre precursor of high compactness, high strength can be obtained by the method
Adopt the solution of the present invention, the polyacrylonitrile carbon fiber precursor obtained, precursor fiber number is 0.6 ~ 1.2dtex, and filament strength is 5 ~ 8cN/dtex, and protonema density is 1.17 ~ 1.19, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
1, stoste preparation: by acrylonitrile (AN), itaconic acid (IA) 97:3, solid content 20% in proportion through distillation; the 0.4wt% that 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) accounts for the 0.4wt% of comonomer, conditioning agent dimethylacetylamide accounts for total inventory; with dimethyl sulfoxide (DMSO) (DMSO) for solvent joins in reactor; under nitrogen protection; react 20 hours under the steady temperature of 38 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, through the filtration of 5 μm of filtering materials, obtains high-performance polyacrylonitrile copolymer spinning solution.After tested, molecular weight is 120021, and molecular weight distribution is 2.34, and viscosity is 57PaS at 60 DEG C.
2, coagulation forming: spinning solution is through measuring pump metering, again after 3 μm are filtered, enter the 1st road coagulating bath after being extruded by spinning head, coagulation bath temperature 20 DEG C, 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: after as-spun fibre is solidified by 3 roads, carries out hot water 3 road drawing-off, and 3 road hot water drawing temperatures are respectively 70 DEG C, 80 DEG C and 90 DEG C, and drafting multiple is respectively 1.2,1.4 and 2..After 3 road hot water drawing-offs, strand carries out 9 road washings, and adopt the mode of ladder-elevating temperature, 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, to 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, once oils subsequently again, 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 6cN/dtex, and precursor density is 1.178.
[embodiment 2]
1, stoste preparation: by acrylonitrile (AN), itaconic acid (IA) 98:2, solid content 20% in proportion through distillation; 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) accounts for 0.6wt%, the conditioning agent N of comonomer; dinethylformamide (DMF) accounts for the 0.2wt% of total inventory; with dimethyl sulfoxide (DMSO) (DMSO) for solvent joins in reactor; under nitrogen protection; react 20 hours under the steady temperature of 38 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, through the filtration of 5 μm of filtering materials, obtains high-performance polyacrylonitrile copolymer spinning solution.After tested, molecular weight is 121451, and molecular weight distribution is 2.21, and viscosity is 64PaS at 60 DEG C.
All the other steps are according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength is 6.3cN/dtex, and precursor density is 1.181.
[embodiment 3]
1, stoste preparation: by acrylonitrile (AN), itaconic acid (IA) 98:2, solid content 22% in proportion through distillation; 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) accounts for 0.6wt%, the conditioning agent N of comonomer; N-dimethylacetylamide (DMAc) accounts for the 0.8wt% of total inventory; with dimethyl sulfoxide (DMSO) (DMSO) for solvent joins in reactor; under nitrogen protection; react 20 hours under the steady temperature of 38 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, through the filtration of 5 μm of filtering materials, obtains high-performance polyacrylonitrile copolymer spinning solution.After tested, molecular weight is 146837, and molecular weight distribution is 2.09, and viscosity is 75PaS at 60 DEG C.
All the other steps are according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength is 6.5cN/dtex, and precursor density is 1.183.
[embodiment 4]
1, stoste preparation: by acrylonitrile (AN), itaconic acid (IA) 99:1, solid content 26% in proportion through distillation; the 1wt% that 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) accounts for the 0.6wt% of comonomer, conditioning agent dimethylacetylamide accounts for total inventory; with dimethyl sulfoxide (DMSO) (DMSO) for solvent joins in reactor; under nitrogen protection; react 20 hours under the steady temperature of 38 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, through the filtration of 5 μm of filtering materials, obtains high-performance polyacrylonitrile copolymer spinning solution.After tested, molecular weight is 189877, and molecular weight distribution is 2.19, and viscosity is 88PaS at 60 DEG C.
All the other steps are according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength is 6.7cN/dtex, and precursor density is 1.185.
[embodiment 5]
1, stoste preparation: by acrylonitrile (AN), itaconic acid (IA) 96:4, solid content 20% in proportion through distillation; 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) accounts for 0.6wt%, the conditioning agent N of comonomer; dinethylformamide (DMF) accounts for the 0.4wt% of total inventory; with dimethyl sulfoxide (DMSO) (DMSO) for solvent joins in reactor; under nitrogen protection; react 20 hours under the steady temperature of 38 DEG C, obtain binary acrylonitrile copolymer spinning fluid.Then spinning solution is after removed under reduced pressure residual monomer and bubble, through the filtration of 5 μm of filtering materials, obtains high-performance polyacrylonitrile copolymer spinning solution.After tested, molecular weight is 116579, and molecular weight distribution is 2.28, and viscosity is 50PaS at 60 DEG C.
All the other steps are according to embodiment 1.
The fiber number of gained precursor is 1.21dtex, and filament strength is 5.3cN/dtex, and precursor density is 1.171.
[embodiment 6]
1, stoste preparation: according to the stoste preparation process of embodiment 1.
2, coagulation forming: spinning solution is through measuring pump metering, again after 3 μm are filtered, enter the 1st road coagulating bath after being extruded by spinning head, coagulation bath temperature 30 DEG C, 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 5.9cN/dtex, and precursor density is 1.176.
[embodiment 7]
1, stoste preparation: according to the stoste preparation process of embodiment 1.
2, coagulation forming: spinning solution measures through measuring pump, again after 3 μm are filtered, enter the 1st road coagulating bath, coagulation bath temperature 40 DEG C by spinning head after being extruded, concentration is 65%, and draw ratio is the-50%, 2nd road coagulating bath is 60 DEG C, concentration is 30%, and draw ratio is the 100%, 3rd road coagulating bath is 60 DEG C, concentration is 20%, draw ratio is the 115%, 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 5.9cN/dtex, and precursor density is 1.176.
[embodiment 8]
1, stoste preparation: according to the stoste preparation process of embodiment 1.
2, coagulation forming: spinning solution is through measuring pump metering, again after 3 μm are filtered, enter the 1st road coagulating bath after being extruded by spinning head, coagulation bath temperature 50 DEG C, 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 6.1cN/dtex, and precursor density is 1.178.
[embodiment 9]
1, stoste preparation: according to the stoste preparation process of embodiment 1.
2, coagulation forming: spinning solution is through measuring pump metering, again after 3 μm are filtered, enter the 1st road coagulating bath after being extruded by spinning head, coagulation bath temperature 60 DEG C, 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: after as-spun fibre is solidified by 3 roads, carries out hot water 3 road drawing-off, and 3 road hot water drawing temperatures are respectively 70 DEG C, 80 DEG C and 90 DEG C, and drafting multiple is respectively 1.2,1.2 and 1.2.After 3 road hot water drawing-offs, strand carries out 9 road washings, and adopt the mode of ladder-elevating temperature, 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, to 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, once oils subsequently again, 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 6.5cN/dtex, and precursor density is 1.178.
[embodiment 10]
1, stoste preparation: according to the stoste preparation process of embodiment 1.
2, coagulation forming: spinning solution is through measuring pump metering, again after 3 μm are filtered, enter the 1st road coagulating bath after being extruded by spinning head, coagulation bath temperature 60 DEG C, 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: after as-spun fibre is solidified by 3 roads, carries out hot water 3 road drawing-off, and 3 road hot water drawing temperatures are respectively 70 DEG C, 80 DEG C and 90 DEG C, and drafting multiple is respectively 1.4,1.6 and 1.8.After 3 road hot water drawing-offs, strand carries out 9 road washings, and adopt the mode of ladder-elevating temperature, 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, to 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, once oils subsequently again, 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 7.8cN/dtex, and precursor density is 1.188.
[embodiment 11]
1, stoste preparation: according to the stoste preparation process of embodiment 1.
2, coagulation forming: spinning solution is through measuring pump metering, again after 3 μm are filtered, enter the 1st road coagulating bath after being extruded by spinning head, coagulation bath temperature 50 DEG C, 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: after as-spun fibre is solidified by 3 roads, carries out hot water 3 road drawing-off, and 3 road hot water drawing temperatures are respectively 70 DEG C, 80 DEG C and 90 DEG C, and drafting multiple is respectively 1.6,2 and 1.8.After 3 road hot water drawing-offs, strand carries out 9 road washings, and adopt the mode of ladder-elevating temperature, 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, to 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, once oils subsequently again, 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 7.9cN/dtex, and precursor density is 1.188.
[embodiment 12]
1, stoste preparation: according to the stoste preparation process of embodiment 1.
2, coagulation forming: spinning solution is through measuring pump metering, again after 3 μm are filtered, enter the 1st road coagulating bath after being extruded by spinning head, coagulation bath temperature 50 DEG C, 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: after as-spun fibre is solidified by 3 roads, carries out hot water 3 road drawing-off, and 3 road hot water drawing temperatures are respectively 70 DEG C, 80 DEG C and 90 DEG C, and drafting multiple is respectively 1.8,1.8 and 2.After 3 road hot water drawing-offs, strand carries out 9 road washings, and adopt the mode of ladder-elevating temperature, 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, to 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, once oils subsequently again, 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 7.6cN/dtex, and precursor density is 1.185.
[comparative example 1]
1, stoste preparation: by acrylonitrile (AN), itaconic acid (IA) 98:2, solid content 20% in proportion through distillation; 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) accounts for the 0.6wt% of comonomer; with dimethyl sulfoxide (DMSO) (DMSO) for solvent joins in reactor; under nitrogen protection; react 20 hours under the steady temperature of 40 DEG C, obtain binary acrylonitrile copolymer spinning fluid.After tested, molecular weight is 134398, and molecular weight distribution is 2.24, and viscosity is 200PaS at 60 DEG C.Stoste viscosity is very large, and gelatin phenomenon is obvious, and after de-single deaeration, carry out 5 μm of filtrations, during filtration, pressure is very large.
2, coagulation forming: spinning solution through measuring pump metering, again after 5 μm are filtered (3 μm of filtrations, head pressure is too high, cannot normally spinning), enter the 1st road coagulating bath after being extruded by spinning head, coagulation bath temperature 60 DEG C, 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: after as-spun fibre is solidified by 3 roads, carries out hot water 3 road drawing-off, and 3 road hot water drawing temperatures are respectively 70 DEG C, 80 DEG C and 90 DEG C, and drafting multiple is respectively 1.6,1.6 and 1.8.After 3 road hot water drawing-offs, strand carries out 9 road washings, and adopt the mode of ladder-elevating temperature, 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, to 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, once oils subsequently again, 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.
Spinning process is unstable, and lousiness is many, and the fiber number of gained precursor is 1.21dtex, and filament strength is 4.5cN/dtex, and precursor density is 1.173.
Claims (10)
1. a preparation method for polyacrylonitrile base carbon fiber precursors, comprises the following steps:
(1) stoste preparation: solvent dimethyl sulfoxide (DMSO), the first monomers acrylonitrile, second comonomer itaconic acid and initator 2,2'-Azobis(2,4-dimethylvaleronitrile), conditioning agent polymerization are obtained spinning solution, spinning solution is after removed under reduced pressure residual monomer and bubble, filtration obtains high-performance polyacrylonitrile copolymer spinning solution, high-performance polyacrylonitrile copolymer spinning solution solid content is 15% ~ 25%, molecular weight is 11 ~ 200,000, molecular weight distribution is 1 ~ 2.5, when 60 DEG C, viscosity is 50 ~ 100PaS, and high-performance polyacrylonitrile copolymer spinning solution temperature is 50 ~ 70 DEG C;
Wherein, molecular weight regulator is selected from least one in dimethylacetylamide, DMF, DMA;
(2) coagulation forming: high-performance polyacrylonitrile copolymer spinning solution, after measuring pump metering, again filtering, through multiple tracks coagulating bath after being extruded, obtains as-spun fibre by spinning head;
(3) drawing-off and washing: as-spun fibre is through the drawing-off of multiple tracks hot water and multiple tracks washing;
(4) to oil and compacting by drying: fiber step (3) obtained, carry out oiling and compacting by drying, the temperature of compacting by drying is 60 ~ 160 DEG C;
(5) steam drafting: the fiber that step (4) obtains is carried out steam drafting, the pressure of steam drafting is 0.1-0.3Mpa, and draw ratio is 1 ~ 4 times;
(6) steam heat sizing and receipts silk: receive silk after the fiber that step (5) obtains is carried out steam heat sizing, obtain high-performance carbon fibre precursor, the pressure of steam heat sizing is 0.1-0.3Mpa.
2. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterized in that raw materials used weight proportion is, 2,2'-Azobis(2,4-dimethylvaleronitrile): the first monomer and second comonomer sum are 0.0040 ~ 0.0080:1, the first monomer and second comonomer sum: gross mass is 0.20 ~ 0.30:1; Acrylonitrile: itaconic acid is 96 ~ 99.9:0.1, conditioning agent: dimethyl sulfoxide (DMSO) is 0.010 ~ 0.10:1.
3. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that removing the mode that residual monomer adopts vacuum removal residual monomer.
4. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterized in that described filter type is Multi-channel filtering, filtering accuracy is 2-5 μm.
5. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterized in that adopting multistage solidification mode, coagulating bath medium is methyl-sulfoxide/aqueous solution, the concentration of coagulating bath adopts ladder concentration to solidify, concentration is between 10%-80%, and the temperature of coagulating bath all controls at 20 ~ 70 DEG C, and the coagulating bath of first road is negative drawing-off, draw ratio is-5% ~-50%, after a few road draw ratio of solidifying be 1 ~ 3.
6. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 5, is characterized in that coagulating bath concentration is between 20% ~ 70%, and the temperature of coagulating bath is 30 ~ 60 DEG C, and the coagulating bath of first road is negative drawing-off, and draw ratio is preferably-20% ~-40%.
7. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterized in that the drawing-off of multiple tracks hot water is that employing 60 ~ 90 DEG C of hot water carry out drawing-off, hot water draw ratio all controls at 1 ~ 3 times.
8. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 7, it is characterized in that multiple tracks washing employing 40 ~ 80 DEG C washing, adopt the mode of ladder-elevating temperature, water rinses does not carry out drawing-off.
9. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, the finish adopted that it is characterized in that oiling is ammonia modified silicon oil, and the concentration of finish is 0.1wt% ~ 1wt%.
10. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that the temperature of compacting by drying is 40 ~ 140 DEG C.
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