CN102965944A - Production method of PAN (Polyacrylonitrile) protofilament - Google Patents
Production method of PAN (Polyacrylonitrile) protofilament Download PDFInfo
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Abstract
The invention discloses a production method of PAN (Polyacrylonitrile) protofilament for producing carbon fibers. The production method comprises the following steps in sequence: oiling the fibers which are obtained by stretching spinning filaments through hot water at the first time by virtue of an oiling agent A, wherein the oiling agent A includes a boron compound and polyester with more than two ester groups; the boron compound occupies 0.1 to 5% based on the mass of all effective compounds of the oiling agent A, except water; drying the fibers after the first oiling; stretching at the same time by steam; and oiling by an oiling agent B at the second time, wherein the oiling agent B contains aromatic polyatomic alcohol and modified polysiloxane; and the modified polysiloxane occupies 5 to 15% based on the mass of the effective components of the oiling agent B. According to the production method of the PAN protofilament, different oiling agents are adopted and used for processing the fibers twice; the boron compound is added to the oiling agent A to reduce the pre-oxidizing speed of the surface layer; the effects of lubricating, static resisting and clustering and the like are given to the fibers; the polyester in the oiling agent B is the aromatic polyester high in heat resistance; and the polyesters can be used for protecting the fibers during pre-oxidizing.
Description
Technical field
The invention provides a kind of PAN(polyacrylonitrile) production method of precursor.
Background technology
The PAN precursor is the raw material of producing carbon fiber, generally is that the PAN precursor is first through pre-oxidation, obtains carbon fiber after the carbonization again.Preoxidation process wherein, the process of exactly the PAN precursor being processed in 200 ~ 300 ℃ of air atmospheres is one of very important link in the carbon fibre manufacturing processes.The PAN precursor does not fire the fiber that does not melt through becoming after the pre-oxidation, makes follow-up high temperature cabonization processing procedure become possibility.But in preoxidation process, exist two problems to have a strong impact on the performance of final carbon fiber, first, the PAN precursor is in the temperature range of pre-oxidation, fiber can soften, can stick together each other between the adjacent monofilament, two of severe patients or many merchandisers silk fiber combine, namely so-called doubling; Second, in preoxidation process, because PAN precursor and oxygen react from fiber surface, thereby the diffusion owing to oxygen is slow between top layer and core, can produce the apparent in view inconsistent phenomenon of the inside and outside extent of reaction, namely form the core-skin dual structure of fiber after the pre-oxidation, the existence of these two problems has a strong impact on PAN precursor pre-oxidation process and carbonisation, so that the unstable carbon fiber that maybe can only obtain poor performance of production process.
For the adhesion doubling phenomena that exists in the preoxidation process, general processing method is that precursor is processed with finish, top layer at monofilament forms the solid film that one deck has good heat resistance, thereby with spaced between the PAN precursor, make it be difficult under the high temperature of pre-oxidation, stick to each other together.The finish that uses generally is to be finish with the polysiloxane-based material of modification as the silicon of main component.But silicon is that the shortcoming of finish is in the heat treatment process of fiber, and the finish volatilization decomposition that is attached on the fiber pollutes equipment, and hydrophobicity is strong, and the homogeneous decentralized on the moistening fiber that obtains after the spinning is bad.And silicon be finish at high temperature, can in pre-oxidation furnace and retort, generate granular silica, palpus shape and tabular silicon nitride, thereby affect the fiber path, make it to narrow down or fully obstruction, cause when processed fiber passes through, owing to rub with body of heater and roller, produce a large amount of lousiness.In addition, in a single day tabular silicon nitride generates in the furnace wall, is difficult to remove, and the result changes the temperature in the retort step by step, causes the carbon fiber quality to descend.Although must shape the crystalline silicon nitride body remove easily, the spicule that comes off is very easily to the carbon fiber injury.In addition, a small amount of element silicon of final residue in carbon fiber has obvious impact to the ablation property of carbon fiber product, therefore must under the prerequisite that does not affect finish basic role and effect, reduce the content of polysiloxane-based material in the former silk oiling agent.
For solving the core-skin dual structure problem of fiber, conventional method is by regulating the copolymerization component of PAN, the compactness of PAN precursor is descended, thereby improve oxygen from the top layer to the diffusion rate of inside, and suitably reduce the pre-oxidation treatment temperature, prolong the processing time, thereby reach relatively consistent inside and outside preoxidation degree.After but PAN precursor compactness descended, also along with descending together, negative effect was too large for intensity, and prolongs the pre-oxidation treatment time, and production efficiency descends, and to the consumption increase of the energy, production cost is also along with raising.
Summary of the invention
The objective of the invention is provides a kind of for overcoming the defective of above-mentioned prior art
PThe production method of AN precursor reduces the content of the polysiloxane-based material in the fibre finishing, is that the drawbacks limit of finish is in minimum with silicon; Reduce simultaneously fiber top layer and core pre-oxidation difference degree, realize the pre-oxidation of homogeneous, improve
PThe performance of AN precursor.
For achieving the above object, the technical solution used in the present invention comprises the steps:
1, the PAN copolymer solution is obtained fiber through behind the wet spinning, with fiber through for the first time drawing-off of hot water, fiber after the drawing-off uses finish A to carry out the oiling treatment first time, finish A contains the polynary ester of organic boron compound and two above ester groups, the quality of boron compound account for finish A dewater outside other active principle quality 0.1 ~ 5%;
2, after the oiling treatment fiber is carried out drying for the first time, dry by for the second time drawing-off of steam, use finish B to carry out the oiling treatment second time after for the second time drawing-off, receive silk after the drying and get final product; Finish B contains the polynary ester of aromatic series and modified polyorganosiloxane, the quality of modified polyorganosiloxane account for finish B dewater outside other active principle quality 5 ~ 15%.
The present invention carries out finish for twice and processes in PAN precursor manufacture process, twice use be different finishes, thereby reach different treatment effects.By in finish A, adding boron-containing compound, make boron element enter the top layer of fiber, reduce the pre-oxidation speed on top layer, process fiber with finish A for the first time, the effects such as lubricated, antistatic, boundling can be provided fiber.Because except modified polyorganosiloxane, polynary ester is the polynary ester of the good aromatic series of heat resistance among the finish B, process fiber with finish B for the second time, can in preoxidation process, can provide protective effect to fiber.Therefore, the present invention has solved the adhesion doubling that exists in the pre-oxidation in the existing PAN base carbon fibre production process and the problem of fiber core-skin dual structure simultaneously.
The specific embodiment
The PAN copolymer solution is obtained fiber through behind the wet spinning, fiber is carried out for the first time drawing-off of hot water, in the flush away fiber, in the remaining solvent fiber is carried out certain drawing-off, improve its molecularly oriented.Fiber after the hot water drawing-off is a kind of material of gel state, and all there are a large amount of micropores in its top layer and inside.Therefore after the hot water drawing-off, fiber is carried out the oiling treatment first time with finish A.The type of service of finish A is water serial emulsion, finish A is the polynary ester that contains the compound of boron element and contain two ester groups, also contain nonionic emulsifier, the skeleton structure of Ester does not have special restriction, can the following array structure formula of concrete example shown in:
Polynary ester the first structural formula of two ester groups is as follows:
Polynary ester the second structural formula of two ester groups is as follows:
Above-mentioned R1 is the alkyl of carbon number 3 ~ 18 to R5, each other can be identical, and also can be different.
If (CH2CH2O-), all be beneficial to for the dispersiveness and the lubricity that improve finish A to the oxyethylene group that 4 ~ 14 additions are arranged between R5 and the ester group at alkyl R1.
The compound that contains boron element is selected water miscible boride, boric acid for example, and the part by weight of boride in finish A active ingredient is 0.1 ~ 5%.Here so-called active ingredient refers in finish A aqueous emulsion, except moisture, and the component that other are all.The present invention introduces the purpose of boride in finish A, because boron element has certain inhibition for pre-oxidation, boron element enters the top layer of fiber by finish A, can reduce the oxidation rate on top layer, under higher oxidizing temperature, produce with oxidation rate faster, and can not produce the core-skin dual structure.If the content of boride in the active ingredient of finish A surpasses 5%, because boron too high levels, it is too large that fiber top layer oxidation rate is reduced, if boride contains quantity not sufficient 0.1% in the active ingredient of finish A, just can not effectively reduce fiber core-skin dual structure.
In the active ingredient of finish A, except the above-mentioned compound that contains boron element with contain the two class materials of polynary ester of two ester groups, can the actual water serial emulsion that uses in order to form, also must comprise emulsifying agent.The selection of emulsifying agent does not have special restriction, as long as above-mentioned ester type compound effectively can be disperseed to form stable emulsion just can, the present invention adopts the emulsifying effectiveness of nonionic emulsifier best, and the stablizing effect after nonionic and the emulsification of anionic compound emulsifying agent is best.
During the finish A oiling treatment first time, generally adopt simple infusion process, after the processing, Ester is attached to the fiber outer wall, and water miscible boron-containing compound then gos deep in the certain thickness zone, fiber top layer from micropore.
Fiber after will processing through finish A be to carry out drying between 120 ~ 150 ℃ in temperature, can adopt the dryings such as contact hot-rolling or contactless baking oven, drying time minimum should be more than 40s.Then the fiber after complete to drying carries out for the second time drawing-off of steam, further improves the degree of orientation and the density of fiber.
Fiber after for the second time drawing-off of steam is carried out the oiling treatment second time with finish B.The type of service of finish B also is water serial emulsion, and finish B contains the polynary ester of aromatic series and modified polyorganosiloxane class material, and the polynary ester here also refers to contain in the molecular structure material of two or more ester groups.Concrete example is as follows:
The polynary ester the first of aromatic series structural formula is as follows:
The polynary ester the second of aromatic series structural formula is as follows:
The R of end group can be the alkyl of carbon number 3 ~ 18 in the said structure formula.If the oxyethylene group (CH of 4 ~ 14 additions is arranged between alkyl Rn and ester group
2CH
2O-), all be beneficial to for the dispersiveness and the lubricity that improve finish.
The structural formula of modified polyorganosiloxane class material is as follows:
Wherein R is amino (R'NH
2), epoxy radicals or polyether segment etc., m, n are unequal positive integer.
In modified polyorganosiloxane class material; must contain amino modified polysiloxanes; this is because amino modified polysiloxane has good film forming, and the solid film that forms after it solidifies has good intensity, can greatly improve the finish film to the protective effect of fiber.
The weight of modified polyorganosiloxane class material in the active ingredient of finish B except moisture accounts for 5 ~ 15%; if less than 5%; film poor heat resistance after finish B solidifies; protection effect in preoxidation process reduces; be difficult to obtain high-intensity fiber; if surpass 15%, will produce adverse consequences.
Fiber after being disposed with finish B is dried again, just can carry out rolling with receiving a silk machine.
Embodiments of the invention below are provided, so that those skilled in the art better understands the present invention, and do not consist of its Copyright law.
Embodiment
With the AN(acrylonitrile) with the IA(itaconic acid) in dimethyl sulfoxide (DMSO), obtain PAN copolymer with the solution polymerization process polymerization according to the ratio of 99.5mol%:0.5mol%, make polymer concentration 21%, the spinning solution of limiting viscosity 1.9.With spinning solution remain on 55 ℃ by the aperture be 0.75mm, hole count be 6000 spinnerets to spray into temperature be 60 ℃, concentration is 60% DMSO(dimethyl sulfoxide (DMSO)) in the aqueous solution.After 4 times of the drawing-offs, A processes with finish in the hot water.Shown in the following tabulation 1 of the composition of finish A and performance.3 times of drawing-offs in the steam under pressure of 0.4MPa behind the fiber drying after the processing.Then fiber is processed with finish B.The composition of finish B and performance are also in table 1.Rolling after the fiber oven dry after the processing.
The precursor that obtains namely has between 200 ~ 300 ℃ of temperature in the pre-oxidation furnace of different warm areas according to known method, carries out pre-oxidation treatment in air atmosphere.To observing its interface with metallographic microscope after the pre-oxidized fibers sampling that obtains, top layer and core are without obvious gray difference.In addition pre-oxidized fibers is cut to the long short fiber of 2cm, it is well dispersed in the water that is added with a small amount of surfactant, then use Filter paper filtering.In microscopically observation doubling situation, be converted to the doubling quantity in each hundred monofilament, average result shows that the doubling number is less than 1.
The component of finish A and finish B sees the following form 1:
Table 1
Claims (3)
1. the production method of a PAN precursor is characterized in that adopting following steps
:
(1) the PAN copolymer solution is obtained fiber through behind the wet spinning, with fiber through for the first time drawing-off of hot water, fiber after the drawing-off uses finish A to carry out the oiling treatment first time, finish A contains the polynary ester of organic boron compound and two above ester groups, the quality of boron compound account for finish A dewater outside other active principle quality 0.1 ~ 5%;
(2) after the oiling treatment fiber is carried out drying for the first time, dry by for the second time drawing-off of steam, use finish B to carry out the oiling treatment second time after for the second time drawing-off, receive silk after the drying and get final product; Finish B contains the polynary ester of aromatic series and modified polyorganosiloxane, the quality of modified polyorganosiloxane account for finish B dewater outside other active principle quality 5 ~ 15%.
2. the production method of a kind of PAN precursor according to claim 1 is characterized in that: step (2) is described, and fiber after the first time oiling treatment is carried out dry temperature is 120 ~ 150 ℃, and drying time is more than 40s.
3. the production method of a kind of PAN precursor according to claim 1, it is characterized in that: finish A also contains nonionic emulsifier.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417393A (en) * | 2002-12-16 | 2003-05-14 | 中国科学院山西煤炭化学研究所 | Prepn of polyacrylonitrile-base high-performance raw carbon fiber |
| JP2010024582A (en) * | 2008-07-22 | 2010-02-04 | Matsumoto Yushi Seiyaku Co Ltd | Finishing agent for acrylic fiber for production of carbon fiber and method for producing carbon fiber by using the same |
| CN101760791A (en) * | 2009-11-24 | 2010-06-30 | 中复神鹰碳纤维有限责任公司 | Method for preparing high-performance polyacrylonitrile-based carbon fiber protofilament through dry spraying and wet spinning |
| CN101956252A (en) * | 2010-09-19 | 2011-01-26 | 东华大学 | Method for preparing carbon fibers from boron modified polyacrylonitrile precursors |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417393A (en) * | 2002-12-16 | 2003-05-14 | 中国科学院山西煤炭化学研究所 | Prepn of polyacrylonitrile-base high-performance raw carbon fiber |
| JP2010024582A (en) * | 2008-07-22 | 2010-02-04 | Matsumoto Yushi Seiyaku Co Ltd | Finishing agent for acrylic fiber for production of carbon fiber and method for producing carbon fiber by using the same |
| CN101760791A (en) * | 2009-11-24 | 2010-06-30 | 中复神鹰碳纤维有限责任公司 | Method for preparing high-performance polyacrylonitrile-based carbon fiber protofilament through dry spraying and wet spinning |
| CN101956252A (en) * | 2010-09-19 | 2011-01-26 | 东华大学 | Method for preparing carbon fibers from boron modified polyacrylonitrile precursors |
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