CN101165237A - Method for preparing polyacrylonitrile-based carbon fiber protofilament - Google Patents
Method for preparing polyacrylonitrile-based carbon fiber protofilament Download PDFInfo
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Abstract
The process of preparing polyacrylonitrile fiber for carbon fiber includes the following steps: soaking resin in deionized water at 20-50 deg.c to swell for 1-2.5 hr; pickling in water solution of nitric acid or hydrochloric acid in pH 0.1-3.0 at 25-60 deg.c for 0.5-1.5 hr; rinsing with deionized water to neutral; dewatering and drying to water content lower than 3 %; dissolving in 35-58 wt% concentration NaSCN aqua to form spinning fluid in resin content of 8-16 wt%; debubbling and spinning to form initial fiber; washing with deionized water, acid aqua and hot water successively; drafting, oiling, drying, densifying, etc to produce polyacrylonitrile fiber for carbon fiber. The polyacrylonitrile fiber product has ash content not higher than 0.01% and alkali metal ion content not higher than 0.005%.
Description
Technical field
The present invention relates to make the method for polyacrylonitrile base carbon fiber precursors, particularly employing is a spinning material with the polyacrylonitrile resin of aqueous suspension polymerization prepared, makes the method for polyacrylonitrile base carbon fiber precursors by solvent spinning technology.
Background technology
Carbon fiber has excellent mechanical property, and other material of specific strength that it is high and specific modulus hardly matches, and as a kind of reinforcing material, it is widely used in the fields such as manufacturing of space flight, airborne vehicle and sports equipment.Carbon fiber is made after pre-oxidation and carbonization by the precursor that carbonizable substance is made usually, because polyacrylonitrile resin has higher carbonization yield, therefore polyacrylonitrile fibre is very desirable carbon fibre precursor, and the carbon fiber that makes thus is called polyacrylonitrile-based carbon fibre.Obtain the carbon fiber of function admirable, the high purifying of precursor is most important.Since metal species impurity after the high-temperature process of pre-oxidation and carbonization still the form with oxide be present in the carbon fiber, so relative non-metal kind impurity, metal species impurity is even more serious to the influence of final carbon fiber product mechanical performance.The impurity of alkali metal class particularly, they have catalytic action to the oxidation of carbon, carry out high temperature such as pre-oxidation, carbonization at precursor when handling, and can promote CO, CO
2Thereby the effusion Deng gas forms cavity blemish in carbon fiber inside.Ash can reflect metal impurities total content in the precursor indirectly, when ash is lower than 0.1 ‰, is generally considered to be high purifying and the content of alkali metal ion is no more than 0.05 ‰ o'clock precursor, and the carbon fiber that makes thus will have higher quality.
Metal species impurity in the polyacrylonitrile base carbon fiber precursors can be from the solvent of polymer raw, polymerization initiation system and polymerization or spinning.In the prior art for the common way of the removal of metal species impurity be last handling process, the precursor of precursor spinning make the back or precursor pre-oxidation after etc. link wash, United States Patent (USP) U.S 4388289 has promptly introduced part technology wherein, and these existing washing means are considered to effective for the impurity from polymer raw and polymerization or spin solvent.And it is generally acknowledged from the difficult method by washing of the impurity of polymerization initiation system and remove, because of they are present on the strand of polymer, but be the polymer molecule interchain that is present in the fiber surface of precursor or fibrous inside from the impurity of polymer raw and polymerization or spin solvent.
The same with the manufacturing of common acrylic fibers, polyacrylonitrile base carbon fiber precursors can adopt the method manufacturing of one-step method, i.e. same solvent is adopted in polymerization and spinning, and polymeric reaction solution directly carries out spinning after regulating concentration; Also can adopt and use the two-step method manufacturing, promptly carry out the preparation of polyacrylonitrile resin earlier, technology commonly used is aqueous suspension polymerization, and the polyacrylonitrile resin that obtains is made spinning solution with solvent again and carried out spinning.Because the polymerization process of two-step method generally adopts redox system, their majorities contain alkali metal, and the polymerization process of one-step method can adopt azo class initiator system, so polyacrylonitrile base carbon fiber precursors adopts the method manufacturing of one-step method basically in the prior art, its objective is in the polymer molecular chain of avoiding precursor to be introduced into alkali metal.But one-step method requires from being polymerized to the production line that spinning forms continuous whole, and this makes the quality control of precursor product and the flexibility of production etc. can not show a candle to two-step method.In the industrial production of common acrylic fibers, one-step method also is used for making on a large scale conventional variety more.With regard to technical process, two-step method obviously is more suitable for the manufacturing in polyacrylonitrile base carbon fiber precursors, just at present still lacks effectively for the removal that is derived from polymerization initiation system impurity in the spinning material polyacrylonitrile resin and is easy to industrialized means.
Summary of the invention
The invention provides a kind of preparation method of polyacrylonitrile base carbon fiber precursors, this method is a spinning material with the polyacrylonitrile resin that makes by aqueous suspension polymerization technology, makes polyacrylonitrile base carbon fiber precursors by solvent spinning technology two-step method.Its technical problem to be solved is to use effectively and is easy to industrialized means and removes the alkali metal class impurity that is derived from initiator system, in the hope of the final polyacrylonitrile base carbon fiber precursors that obtains high purifying.
Below be the detailed technical scheme of the present invention:
A kind of preparation method of polyacrylonitrile base carbon fiber precursors, this method is spinning material with the polyacrylonitrile resin, it may further comprise the steps successively:
1) polyacrylonitrile resin places deionized water to soak swelling 1～2.5 hour, and water temperature is controlled to be 20～50 ℃;
2) polyacrylonitrile resin is placed aqueous acid impose stirring and carry out pickling, nitric acid or hydrochloric acid are adopted in acid, and the pH value of aqueous acid is 0.1～3.0, and the weight ratio of polyacrylonitrile resin and aqueous acid is 1: (4～20), pickling temperature is 25～60 ℃, and the pickling time is 0.5～1.5 hour;
3) polyacrylonitrile resin is extremely neutral with rinsed with deionized water, rinsing temperature is 25～60 ℃;
4) polyacrylonitrile resin is dewatered and is dry, makes it moisture content and is lower than 3%;
5) polyacrylonitrile resin is dissolved in and makes spinning solution in the solvent, and solvent is the NaSCN aqueous solution of 35～58wt%, and polyacrylonitrile resin content is 8～16wt% in the spinning solution;
6) spinning solution sprays silk after removing bubble, is as-spun fibre through the coagulating bath solidification forming, and coagulating bath is the NaSCN aqueous solution of 8～16wt%, and coagulation bath temperature is-5～16 ℃;
7) as-spun fibre deionized water drip washing, water temperature are 45～65 ℃, and the drip washing time is 2～18 minutes;
8) as-spun fibre carries out pickling through acid rinse bath, and nitric acid or hydrochloric acid are adopted in acid, and the pH value of acid rinse bath is 0.5～3.0, and temperature is 30～60 ℃, and the pickling time is 2～15 minutes;
9) rinsing is carried out in the hot bath of as-spun fibre process deionized water, and the hot bath temperature is 45～98 ℃, and the rinsing time is 4～20 minutes;
10) as-spun fibre is made the polyacrylonitrile base carbon fiber precursors product through last handling process, and last handling process comprises drawing-off, oils and compacting by drying.
Above-mentioned steps 1 described water temperature preferably is controlled to be 30～40 ℃.
The pH value of above-mentioned steps 2 described aqueous acids is preferably 0.3～1.6; The weight ratio of polyacrylonitrile resin and salpeter solution is preferably 1: (4～12); Pickling temperature is preferably 35～45 ℃.
Above-mentioned steps 3 described rinsing temperatures are preferably 40～50 ℃.
Above-mentioned steps 7 described drip washing water temperatures are preferably 50～60 ℃; The drip washing time is preferably 4～8 minutes.
The pH value of above-mentioned steps 8 described acid rinse baths is preferably 1.0～3.0; Temperature is preferably 40～55 ℃; The pickling time is 4～8 minutes.
Above-mentioned steps 9 described hot bath temperature are preferably 50～60 ℃, and the rinsing time is preferably 4～8 minutes.
Drawing-off in the above-mentioned steps 10 described last handling processes is preferably the hot bath drawing-off, and the described rinsing of step 9 this moment can merge with drawing-off to be carried out, and promptly the heating drafting process of the rinse cycle of as-spun fibre in the drawing-off hot bath carries out simultaneously.The drawing-off hot bath is a deionized water, and drawing-off hot bath temperature is with rinsing hot bath temperature, and the time of staying of as-spun fibre in the drawing-off hot bath is with the rinsing time.
In the technical program, polyacrylonitrile resin makes with aqueous suspension polymerization technology, the initator of polymerization is water miscible Oxidizing and Reducing Agents, and wherein oxidant is a kind of in ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide or the sodium chlorate, or two or more mixtures; Reductant is a kind of in sodium pyrosulfite, sodium hydrogensulfite or the sodium sulfite, or two or more mixtures.
The same with prior art, above-mentioned polyacrylonitrile resin is the copolymer of acrylonitrile and other vinyl monomer, acrylonitrile generally is at least 95wt% in the comonomer, other monomer comprises first comonomer and second comonomer, its effect is respectively drawing-off property modification and stabilizing modification, the former can be methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate or vinylacetate etc., and the latter can be methacrylic acid, acrylic acid, itaconic acid, acrylamide or Methacrylamide etc.
Although being derived from the alkali metal impurity of initiator system is present in the polyacrylonitrile strand, but be positioned at the end of the chain of strand after all, theoretically, this is positioned at the strand middle part than impurity removes easily, and the structure of strand can not destroyed because of the removal of impurity yet.Key of the present invention is the washing of being carried out before polyacrylonitrile resin dissolving, and inventor's discovery is washed the metal impurities from polymer raw, polymerization process in this link, and it is all very effective to be derived from the removal of initiator system alkali metal impurity.The polyacrylonitrile resin that is obtained by aqueous polymerization is powdery, and bigger specific surface is obviously favourable to washing, but also is easy to generate negative influence simultaneously.Therefore the design of washing process just seems extremely important, comprise washing and pickling the mode that hockets, sour selection, wash condition of each step or the like.If acid intensity, wash temperature and time etc. of acidic cleaning liquid are integrated are interpreted as washing intensity, then crossing in the low washing intensity precursor may still remaining more alkali metal impurity, and the washing intensity too high polyacrylonitrile resin that may make is partly dissolved, even causes the polyacrylonitrile resin molecule oxidized etc.By a large amount of experiments, the inventor has determined the described washing strength range of washing process in the technique scheme, experimental data shows, can remove alkali metal impurity effectively in the washing that this scope is carried out, and can guarantee that polyacrylonitrile resin does not take place by dissolving or not oxidized, the destruction that perhaps suffers other form.
It is that solvent is made spinning solution that polyacrylonitrile resin after the washing adopts the NaSCN aqueous solution, and spinning process adopts conventional wet processing, and the last handling process of as-spun fibre is also basic identical with prior art.Because solvent contains sodium ion, therefore must clean as-spun fibre, to remove the metal species impurity that spinning process is brought by solvent, cleaning process comprises hot water drip washing, pickling and rinsing.Also in this process, removed substantially by the little metal impurity that equipment is introduced.
Compared with prior art, advantage of the present invention be adopted a kind of effectively and be easy to the alkali metal impurity means that industrialized removal is derived from initiator system, thereby can adopt the polyacrylonitrile resin that makes with aqueous suspension polymerization technology is raw material, makes the polyacrylonitrile base carbon fiber precursors of high-purityization by solvent spinning technology two-step method.
In addition, in the technology of one-step method, generally can only carry out behind fibre forming for the removal of metal species impurity, and fiber solidified the rear surface and formed more solid cortex this moment, this makes fibrous inside and outside mass exchange difficulty more.And the present invention washs polyacrylonitrile resin earlier before spinning solution is made, for the fiber of solidification forming, the resin of powdery obviously more helps inner with outside mass exchange, and is therefore also more thorough for the removal from the metal species impurity of polymer raw and polymerization process.
The precursor product ash that the present invention makes can be reduced to below 0.1 ‰, and the content of alkali metal ion is lower than 0.05 ‰.
Below will the invention will be further described by specific embodiment, because the last handling process and the prior art of preparation, spinning and the as-spun fibre of spinning solution are basic identical in the present invention, and known by those of ordinary skill in the art, so embodiment will pay attention to the process conditions of polyacrylonitrile resin washing process and as-spun fibre washing process are enumerated.
In an embodiment, metal element content adopts flame atomic absorption spectrometry, and the assay method of ash is as described below:
Get sample (being accurate to 0.0001g) about 2g and place porcelain crucible, the crucible that sample is housed is placed on the electric furnace temperature heating 10～30min to be no more than 120 ℃, evaporate the water through 800 ℃ of temperature calcinations.Treat that filter paper is firing, crucible put into 800 ℃ high temperature resistance furnace after the dryness residue occurring, calcination 30min makes it ashing, after taking out from high temperature furnace, moves in the drier and is cooled to room temperature, weighs.And be calculated as follows:
In the formula: m
1Be ash content quality (g) after the style calcination, m is sample mass (g).
The specific embodiment
The spinning material polyacrylonitrile resin that embodiment adopts makes by aqueous suspension polymerization technology, and second, third comonomer except that acrylonitrile is respectively methyl acrylate and itaconic acid, and three's the weight ratio that feeds intake is 97: 2: 1.The initiator system of polymerization is a redox system, and wherein oxidant is a sodium chlorate, and reductant is a sodium pyrosulfite.
The ash that records the polyacrylonitrile resin raw material is that 1.62 ‰, Na ion concentrations are 0.25 ‰.
[embodiment 1～10]
Place deionized water to soak swelling above-mentioned spinning material polyacrylonitrile resin, water temperature is controlled at required temperature range, and unnecessary moisture content was sloughed in taking-up after immersion was swelling to the required time.The process conditions of soaking swelling see Table 1;
Polyacrylonitrile resin through soaking swelling places aqueous acid, imposes to stir to carry out pickling.Embodiment 1～8 adopts nitric acid, and embodiment 9～10 adopts hydrochloric acid, and other acid cleaning process condition sees Table 1;
Then that polyacrylonitrile resin is extremely neutral with rinsed with deionized water, rinsing temperature sees Table 1;
At last with the polyacrylonitrile resin vacuum filtering and dewatering, and under 80～100 ℃ of temperature, carry out drying, be lower than 3% until the moisture content of resin
Measure the ash and the Na ion concentration of polyacrylonitrile resin, the results are shown in Table 2.
Table 1.
* weight ratio=polyacrylonitrile resin: aqueous acid
Table 2.
| Resin ash (‰) | Resin Na ion concentration (‰) | |
| Embodiment 1 | 0.099 | 0.050 |
| Embodiment 2 | 0.098 | 0.045 |
| Embodiment 3 | 0.098 | 0.041 |
| Embodiment 4 | 0.090 | 0.050 |
| Embodiment 5 | 0.089 | 0.042 |
| Embodiment 6 | 0.089 | 0.048 |
| Embodiment 7 | 0.080 | 0.032 |
| Embodiment 8 | 0.082 | 0.040 |
| Embodiment 9 | 0.099 | 0.043 |
| Embodiment 10 | 0.099 | 0.041 |
[embodiment 11～17]
Polyacrylonitrile resin through embodiment 1～10 carrying out washing treatment adopts conventional technology to carry out solvent spinning, and steps in sequence is:
Resin after embodiment 1～10 carrying out washing treatment is mixed, be dissolved in and make spinning solution in the solvent, solvent is the NaSCN aqueous solution of 35～58wt%, polyacrylonitrile resin content is 8～16wt% in the spinning solution;
Spinning solution sprays silk after removing bubble, is as-spun fibre through the coagulating bath solidification forming, and coagulating bath is the NaSCN aqueous solution of 8～16wt%, and coagulation bath temperature is controlled between-5～16 ℃;
As-spun fibre deionized water drip washing, water temperature and drip washing time see Table 3;
As-spun fibre carries out pickling through acid rinse bath, and nitric acid or hydrochloric acid are adopted in acid, and wherein embodiment 11～14 and 16～18 is a nitric acid, and embodiment 15 is a hydrochloric acid.The pH value of acid rinse bath, temperature, pickling time see Table 3;
Rinsing is carried out in the hot bath of as-spun fibre process deionized water, and hot bath temperature, rinsing time see Table 3;
As-spun fibre through drawing-off, oil and last handling process such as compacting by drying, obtaining fiber number is the polyacrylonitrile base carbon fiber precursors product of 1.22dtex.
Measure the ash and the Na ion concentration of precursor, the results are shown in Table 4.
[embodiment 18]
As-spun fibre directly enters drawing-off after finishing pickling, and drawing-off is the hot bath heating, and the heating drafting process of rinse cycle in the drawing-off hot bath carries out simultaneously.The drawing-off hot bath is a deionized water, and drawing-off hot bath temperature is with rinsing hot bath temperature, and the time of staying of as-spun fibre in the drawing-off hot bath, its process conditions were listed in table 3 with the rinsing time.
Except above-mentioned points, all the other are with embodiment 11～15.Measure the ash and the Na ion concentration of precursor product, the results are shown in Table 4.
Table 3.
Table 4.
| Precursor ash (‰) | Precursor Na ion concentration (‰) | |
| Embodiment 11 | 0.082 | 0.041 |
| Embodiment 12 | 0.072 | 0.037 |
| Embodiment 13 | 0.078 | 0.039 |
| Embodiment 14 | 0.075 | 0.040 |
| Embodiment 15 | 0.080 | 0.042 |
| Embodiment 16 | 0.079 | 0.038 |
| Embodiment 17 | 0.080 | 0.032 |
| Embodiment 18 | 0.062 | 0.031 |
Claims (10)
1. the preparation method of a polyacrylonitrile base carbon fiber precursors, this method is a spinning material with the polyacrylonitrile resin, it may further comprise the steps successively:
1) polyacrylonitrile resin places deionized water to soak swelling 1～2.5 hour, and water temperature is controlled to be 20～50 ℃;
2) polyacrylonitrile resin is placed aqueous acid impose stirring and carry out pickling, nitric acid or hydrochloric acid are adopted in acid, and the pH value of aqueous acid is 0.1～3.0, and the weight ratio of polyacrylonitrile resin and aqueous acid is 1: (4～20), pickling temperature is 25～60 ℃, and the pickling time is 0.5～1.5 hour;
3) polyacrylonitrile resin is extremely neutral with rinsed with deionized water, rinsing temperature is 25～60 ℃;
4) polyacrylonitrile resin is dewatered and is dry, makes it moisture content and is lower than 3%;
5) polyacrylonitrile resin is dissolved in and makes spinning solution in the solvent, and solvent is the NaSCN aqueous solution of 35～58wt%, and polyacrylonitrile resin content is 8～16wt% in the spinning solution;
6) spinning solution sprays silk after removing bubble, is as-spun fibre through the coagulating bath solidification forming, and coagulating bath is the NaSCN aqueous solution of 8～16wt%, and coagulation bath temperature is-5～16 ℃;
7) as-spun fibre deionized water drip washing, water temperature are 45～65 ℃, and the drip washing time is 2～18 minutes;
8) as-spun fibre carries out pickling through acid rinse bath, and nitric acid or hydrochloric acid are adopted in acid, and the pH value of acid rinse bath is 0.5～3.0, and temperature is 30～60 ℃, and the pickling time is 2～15 minutes;
9) rinsing is carried out in the hot bath of as-spun fibre process deionized water, and the hot bath temperature is 45～98 ℃, and the rinsing time is 4～20 minutes;
10) as-spun fibre is made the polyacrylonitrile base carbon fiber precursors product through last handling process, and last handling process comprises drawing-off, oils and compacting by drying.
2. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that the described water temperature of step 1 is controlled to be 30～40 ℃.
3. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, the pH value that it is characterized in that the described aqueous acid of step 2 is 0.3～1.6, the weight ratio of polyacrylonitrile resin and salpeter solution is 1: (4～12).
4. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that the described pickling temperature of step 2 is 35～45 ℃.
5. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that the described rinsing temperature of step 3 is 40～50 ℃.
6. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that the described water temperature of step 7 is 50～60 ℃, and the drip washing time is 4～8 minutes.
7. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, the pH value that it is characterized in that the described acid rinse bath of step 8 is 1.0～3.0, and temperature is 40～55 ℃, and the pickling time is 4～8 minutes.
8. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1 is characterized in that the described hot bath temperature of step 9 is 50～60 ℃, and the rinsing time is 4～8 minutes.
9. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, it is characterized in that the drawing-off in the described last handling process of step 10 is the hot bath drawing-off, described rinsing of step 9 and drawing-off merge to be carried out, the drawing-off hot bath is a deionized water, drawing-off hot bath temperature is with rinsing hot bath temperature, and the time of staying of as-spun fibre in the drawing-off hot bath is with the rinsing time.
10. according to the preparation method of claim 1～8 or 9 described polyacrylonitrile base carbon fiber precursors, it is characterized in that described polyacrylonitrile resin makes with aqueous suspension polymerization technology, the initator of polymerization is water miscible Oxidizing and Reducing Agents, wherein oxidant is a kind of in ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide or the sodium chlorate, or two or more mixtures; Reductant is a kind of in sodium pyrosulfite, sodium hydrogensulfite or the sodium sulfite, or two or more mixtures.
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| GB1600640A (en) * | 1977-05-26 | 1981-10-21 | Hitco | Method of removing alkali and alkaline earth impurities from carbonizable polyacrylonitrile material |
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