CN102953139B - The preparation method of polyacrylonitrile base carbon fiber precursors - Google Patents
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Abstract
A kind of preparation method of polyacrylonitrile base carbon fiber precursors, spinning material polyacrylonitrile resin Third monomer is furoate clothing, comprise successively: resin NaSCN solution becomes spinning solution, adopt wet spinning technology to obtain as-spun fibre through spray silk and solidification forming; As-spun fibre carries out water-bath drawing-off and uses deionized water drip washing in the NaSCN aqueous solution; The cushioning liquid that as-spun fibre is placed in containing sour A and salt B floods, and A is sulfuric acid, hydrochloric acid or nitric acid, and B is sodium salt or the sylvite of A; As-spun fibre carries out water-bath drawing-off in pure water; As-spun fibre to be placed in after acidic aqueous solution dipping again by rinsed with deionized water to rinsing liquid in neutral; Through to oil and the last handling process such as compacting by drying makes polyacrylonitrile base carbon fiber precursors product.The technical problem that the present invention solves is the object being reached precursor purifying by washing, and fibrous fracture intensity is unaffected simultaneously, compensate for the defect that prior art exists.
Description
Technical field
The present invention relates to and manufacture the method for polyacrylonitrile base carbon fiber precursors, particularly using adopts furoate clothing be the polyacrylonitrile resin of the 3rd comonomer as spinning material, by the method for solution spinning processes manufacture polyacrylonitrile base carbon fiber precursors.
Background technology
Carbon fiber has excellent mechanical property, and its high specific strength and other material of specific modulus hardly match, and as a kind of reinforcing material, it is widely used in the field such as manufacture of space flight, airborne vehicle and sports equipment.The precursor that carbon fiber is made up of carbonizable substance is usually obtained after pre-oxidation and carbonization, because polyacrylonitrile resin has higher carbonization yield, therefore polyacrylonitrile fibre is ideal carbon fibre precursor, and obtained carbon fiber is called polyacrylonitrile-based carbon fibre.
Obtain the polyacrylonitrile-based carbon fibre of function admirable, the purifying of precursor is most important, especially higher to the requirement of metals content impurity, as alkali and alkaline earth metal ions, they are when precursor carries out the high-temperature process such as pre-oxidation, carbonization, can promote the effusion of the gases such as CO, CO2 thus form cavity blemish in carbon fiber inside.If measure metals content impurity in precursor with ash, when ash lower than 0.1 ‰ time precursor be generally considered to be High Purity, carbon fiber obtained thus will have higher quality.
Metal species impurity in polyacrylonitrile base carbon fiber precursors is mainly from the solvent of polymer raw, polymerization initiation system and polymerization or spinning.For metal impurities removal can after the last handling process of precursor manufacture, precursor are made or the precursor link such as after pre-oxidation adopt the means of washing to carry out, prior art is generally first washed with acidic aqueous solution, then carries out rinsing with deionized water.US Patent No. 3,413,094, US4,113,847, US4,507,272 describe portion of techniques wherein respectively, " the fine pickling of carbon fiber precursor of PAN base and the discussion of ion diffuse mechanism " [" Donghua University's journal (natural science edition) " 06 phase in 1993] literary composition then washs PAN as-spun fibre, finished fiber and pre-oxidized fibers, and the factors such as wash temperature, acid strength, time, stirring and fiber hole have done detailed elaboration for the relation etc. of clean result.The current industrial purification impurity elimination process usually just completed before pre-oxidation precursor, because metal impurities can damage the structure of preoxided thread when pre-oxidation.
The same with the manufacture of common acrylic fibers, the spinning material polyacrylonitrile resin of polyacrylonitrile base carbon fiber precursors is not the homopolymers of a kind of monomer polymerization of acrylonitrile, it must containing the second comonomer of about 2 ~ 5wt%, conventional as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate or vinylacetate etc.The existence of second comonomer can destroy the macromolecular regularity of polyacrylonitrile, reduces intermolecular active force thus the drawing-off of as-spun fibre can be carried out smoothly.In addition, it also contains the Third monomer of 0.5 ~ 2.0wt%, the most frequently used is itaconic acid, the existence of itaconic acid can change the thermal cyclization reaction behavior of polyacrylonitrile when pre-oxidation, reduce oxidation reaction initial temperature and peak temperature, make oxidation reaction heat release mild, Wen Fenggeng is wide, oxidizing process is carried out more thorough, and this is conducive to the mechanical performance improving carbon fiber.
Current polyacrylonitrile carbon fiber precursor still more adopts inorganic salts or aqueous acid to be solvent spinning technique manufacture in a wet process, and conventional inorganic salts or acid comprise NaSCN, Zncl
2and HNO
3deng, wherein the industrial applications of NaSCN is the most general.In prior art, the purge process of precursor mainly comprises acid solution washing and rinsing two steps, and fiber first carries out dipping washing with the metal impurities in clean fiber with acidic aqueous solution, then with deionized water, fiber rinsing is extremely neutral.It is generally acknowledged that before as-spun fibre does not complete drawing-off, carry out washing has good effect, because now fiber still locates gel state, structure is comparatively loose, and the metal ion of fibrous inside easily spreads to cleaning solution.This washing methods is ideal for removing the effect of metal impurities in fiber, but can bring the drawing-off of fiber unfavorable.This be due to metal impurities thoroughly clean after, polyacrylonitrile macromolecular chain underpants health acid unit is carboxylic acid by the Forms Transformation of carboxylate.We know, the hydrogen atom on carboxylic acid presents positive charge because electronics departs from, and it can form hydrogen bond by the nitrogen-atoms large with electronegativity in acrylonitrile unit in strand.This hydrogen bond can be present in same macromolecular chain makes moiety segments Cheng Huan, and the adjacent macromolecular moiety segments of chien shih that also can be present in different large molecule is cross-linked.Because the adhesion of hydrogen bond is much larger than general intermolecular model Dehua gravitation, this will cause fiber polymer macromolecule when drawing-off to be difficult to be stretched stretching, and the desired result of drawing of fiber makes all polymer macromolecules be straightened under the effect of external force and obtain the higher degree of orientation.Experiment shows, under draft ratio and the identical prerequisite of other process conditions, after pickling, the drawing-off of as-spun fibre can become comparatively difficulty, and the TENSILE STRENGTH of precursor product also presents downward trend, and extension at break is in rising trend simultaneously.Usual single fiber extension at break rises about about 5%, and the lower reduction of broken filament intensity is then more obvious, generally can reach about 15%, and this can have a strong impact on the mechanical performance of carbon fiber finished product undoubtedly.As-spun fibre carries out washing then purification effect again after completing drawing-off desirable not to the utmost, because now fibre structure is comparatively tight, is unfavorable for that metal ion spreads to cleaning solution.Particularly the dissociation constant of alkali earth metal is relatively low, be in Fibrous depth to be difficult to be removed by pickling with the alkaline-earth metal ions that carboxylate form exists, even if strengthening washing process condition, in precursor product, ash is still difficult to reach the level lower than 0.1wt ‰ under normal circumstances.Up to now, prior art not yet effectively solves purifying and this contradiction of mechanical degradation of above-mentioned precursor.
Summary of the invention
The invention provides a kind of preparation method of polyacrylonitrile base carbon fiber precursors, spinning material is adopt furoate clothing to be the polyacrylonitrile resin of the 3rd comonomer, and adopts NaSCN aqueous solution wet spinning technology.Technical problem to be solved by this invention is that precursor passes through to wash the object reaching purifying, and fibrous fracture intensity is unaffected simultaneously, thus makes up the defect of prior art existence.
Below that the present invention solves the problems of the technologies described above concrete technical scheme:
A preparation method for polyacrylonitrile base carbon fiber precursors, spinning material polyacrylonitrile resin is the copolymer of three kinds of monomers, and the first monomer is acrylonitrile; Second comonomer takes from the one in methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate or vinylacetate; Third monomer is furoate clothing.In polyacrylonitrile resin, the content of Third monomer is 0.5 ~ 2.0wt%, and second and the total content of Third monomer be 1.0 ~ 7.0wt%.
This preparation method comprises the following steps successively:
1) polyacrylonitrile resin with the NaSCN aqueous solution of 45 ~ 58wt% for solvent is mixed with spinning solution, with the NaSCN aqueous solution of 8 ~ 16wt% for coagulating bath adopt wet spinning technology through spray silk and solidification forming obtain as-spun fibre;
2) as-spun fibre carries out water-bath drawing-off in the NaSCN aqueous solution of 1 ~ 5wt%, and it is 5 ~ 30 DEG C that bath temperature controls, and it is 1.5 ~ 2.5 that drafting multiple controls;
3) as-spun fibre deionized water drip washing, it is 45 ~ 60 DEG C that water temperature controls, and drip washing time controling is 2 ~ 20min;
4) cushioning liquid that as-spun fibre is placed in containing sour A and salt B floods, A is nitric acid, sulfuric acid or hydrochloric acid, B is sodium salt or the sylvite of A, the pH value of cushioning liquid is 0.5 ~ 3.0, the concentration of sodium ion or potassium ion is 200 ~ 800mg/L, and the temperature of cushioning liquid controls to be 45 ~ 60 DEG C, with mass ratio range; bath raio controls as as-spun fibre: cushioning liquid=1: (15 ~ 25), and it is 2 ~ 15min that dip time controls;
5) as-spun fibre carries out water-bath drawing-off in pure water, and it is 95 ~ 100 DEG C that bath temperature controls, and it is 3 ~ 5 that drafting multiple controls;
6) as-spun fibre is placed in acidic aqueous solution and floods, acid adopts nitric acid, sulfuric acid or hydrochloric acid, the pH value of acidic aqueous solution is 3.0 ~ 5.0, it is 45 ~ 60 DEG C that temperature controls, with mass ratio range; bath raio controls as as-spun fibre: solution=1: (15 ~ 25), and it is 2 ~ 8min that dip time controls;
7) as-spun fibre temperature is that the deionized water of 90 ~ 100 DEG C carries out hot bath rinsing, until rinsing liquid is in neutral;
8) as-spun fibre makes polyacrylonitrile base carbon fiber precursors product through last handling process, and last handling process comprises and oiling and compacting by drying.
Above-mentioned steps 4) described in A be preferably nitric acid, B is preferably sodium nitrate; The pH value of cushioning liquid is preferably 1.0 ~ 2.0; The concentration of sodium ion or potassium ion is preferably 300 ~ 500mg/L; The temperature of cushioning liquid is preferably 45 ~ 55 DEG C; Bath raio preferably controls as as-spun fibre: cushioning liquid=1: (18 ~ 23); Dip time preferably controls to be 4 ~ 8min.
Above-mentioned steps 6) described in the pH value of acidic aqueous solution be preferably 3.5 ~ 4.5; The temperature of acidic aqueous solution preferably controls to be 50 ~ 55 DEG C; Bath raio preferably controls as as-spun fibre: solution=1: (18 ~ 23); Dip time preferably controls to be 3 ~ 5min.
In above-mentioned bath raio, as-spun fibre weight can press the pure calculating of polyacrylonitrile resin content in spinning solution again according to the spinning solution extrusion capacity of spinning part.
Same as the prior art, the molecular weight of above-mentioned polyacrylonitrile resin is generally 50000 ~ 200000; Above-mentioned steps 1) described in spinning solution in polyacrylonitrile resin content general control be 10 ~ 14wt%.
Essence of the present invention is when as-spun fibre carries out washing removal metal impurities, the acid solution that cleaning solution is generally adopted by prior art is changed into a kind of cushioning liquid containing inorganic acid and corresponding sodium salt or sylvite.Before washing step is positioned at drawing-off, as-spun fibre is after the washing of cushioning liquid dipping, be free on large intermolecular metal impurities in fiber to be removed by washing under the action of an acid, alkaline earth metal atom on the furoate clothing unit existed with carboxylate form in large molecule is then buffered sodium ion in solution or potassium ion replaces, become sodium salt or sylvite, and be not converted into carboxylic acid.As-spun fibre carries out drawing-off immediately after the washing of cushioning liquid dipping, and the nitrogen-atoms due to the hydrogen atom on the hydroxy-acid group of furoate clothing unit and acrylonitrile unit forms hydrogen bond and avoided, and the large molecule of curling at random can successfully be straightened when drawing-off orientation.
Sodium ion or potassium ion are cleaned with acid solution after completing drawing-off by as-spun fibre again, and then carry out rinsing with deionized water.Because sodium ion or potassium ion have higher dissociation constant, the as-spun fibre completing drawing-off can reach the object that the sodium ion brought into by cushioning liquid or potassium ion are cleaned completely after pickling again and rinsed with deionized water.Inventor is confirmed by experimental data, and as-spun fibre carries out pickling and rinsing by the process conditions described in technical solution of the present invention after completing drawing-off, and the ash of precursor product substantially all can lower than 0.1 ‰.
The acid selected in cushioning liquid is commonly used by during prior art pickling, as long as sodium salt or sylvite have good water-soluble and easy ionization analyst in theory, but for making rinsing process more easy to control, acid and salt should be got both and have identical acid group.
Although the present invention only adopts the NaSCN aqueous solution to be spin solvent, those skilled in the art is not difficult to know by inference, and other manufactures the conventional inorganic solvent of polyacrylonitrile fibre as HNO
3, Zncl
2deng being applicable to the technical program too.
Compared with prior art the present invention achieves substantial progress, and fiber reaches by washing is satisfactory the object removing metal impurities, and purification effect is very good.The drawing-off of fiber then can be smooth, and the broken filament intensity of precursor product can improve about 10 ~ 20% relatively, and single fiber extension at break can reduce about 5 ~ 10%, and invention effect is very obvious.
Below by specific embodiment, the invention will be further described.Because washing process is main distinguishing feature of the present invention, spinning material, other spinning and aftertreatment technology etc. are all substantially identical with prior art, therefore embodiment and comparative example will focus on enumerating of washing process and draft process condition especially, and correspondingly show reflection washing and the testing performance index data of drawing-off effect, as the ash of precursor, broken filament intensity and extension at break.There is not obvious relevance in other conventional index of precursor and distinguishing characteristics of the present invention, embodiment and comparative example are by it will not go into details.
In embodiment and comparative example, broken filament intensity and extension at break are pressed GB/T14335-2008 and are measured, under the assay method of ash is shown in:
Get the sample (quality is m, is accurate to 0.0001g) of about 4g, be placed in through 800 DEG C of temperature calcinations that (quality is m to constant weight
0) porcelain crucible in, the crucible that sample is housed is placed on electric furnace heat 10 ~ 30min, burn to sample ashing without black smoke.On electric furnace, cooling for a moment, then put into the high temperature resistance furnace of 800 DEG C, and calcination 2hr makes it ashing, and after taking out from high temperature furnace, move in drier and be cooled to room temperature, weighing, (quality is m
1).
Be calculated as follows ash:
Detailed description of the invention
The spinning material polyacrylonitrile resin that embodiment and comparative example adopt is obtained by aqueous suspension polymerization technique, second, third comonomer except acrylonitrile is respectively methyl acrylate and itaconic acid, the weight ratio of three is 97: 2: 1, and the molecular weight of acrylonitrile resin is 90000.The ash recording polyacrylonitrile resin raw material is 1.62 ‰.
[embodiment 1 ~ 12]
Carry out the preparation of carbon fibre precursor according to the following steps:
1) polyacrylonitrile resin is with the NaSCN aqueous solution of 45 ~ 58wt% for solvent is mixed with spinning solution, and in spinning solution, polyacrylonitrile resin content is 10 ~ 14wt%.With the NaSCN aqueous solution of 8 ~ 16wt% for coagulating bath adopts wet spinning technology to obtain as-spun fibre through spray silk and solidification forming;
2) as-spun fibre carries out water-bath drawing-off in the NaSCN aqueous solution of 1 ~ 5wt%, and this step, in table 1, is defined as front draft in table by the bath temperature of each embodiment and drafting multiple;
3) as-spun fibre deionized water drip washing, it is 45 ~ 60 DEG C that water temperature controls, and drip washing time controling is 2 ~ 20min;
4) cushioning liquid that as-spun fibre is placed in containing sour A and salt B floods, and the control data of the temperature of each embodiment cushioning liquid composition and pH value, cushioning liquid, bath raio and dip time etc. is in table 2 and 3;
5) as-spun fibre carries out water-bath drawing-off in pure water, and this step, in table 1, is defined as first break draft in table by the control data of each embodiment bath temperature and drafting multiple;
6) as-spun fibre is placed in acidic aqueous solution and floods, and the control data of the acid that each embodiment acidic aqueous solution adopts, pH value and temperature, bath raio, dip time etc. is in table 4;
7) as-spun fibre temperature is that the deionized water of 90 ~ 100 DEG C carries out hot bath rinsing, until rinsing liquid is in neutral;
8) as-spun fibre is through oiling and the last handling process such as compacting by drying, obtains the polyacrylonitrile base carbon fiber precursors product that fiber number is 1.22dtex.
[comparative example 1 ~ 4]
Carry out the preparation of carbon fibre precursor according to the following steps:
1) ~ 3) identical with embodiment 1 ~ 12, each comparative example step 2) bath temperature and drafting multiple in table 1;
4) as-spun fibre is placed in acidic aqueous solution and floods, and the control data of the acid that each comparative example acidic aqueous solution adopts, pH value, temperature, bath raio and dip time etc. is in table 2 and 3;
5) as-spun fibre temperature is that the deionized water of 90 ~ 100 DEG C carries out hot bath rinsing, to rinsing liquid in neutral;
6) as-spun fibre carries out water-bath drawing-off in pure water, and this step, in table 1, is defined as first break draft in table by the control data of each comparative example bath temperature and drafting multiple;
7) as-spun fibre is through oiling and the last handling process such as compacting by drying, obtains the polyacrylonitrile base carbon fiber precursors product that fiber number is 1.22dtex.
Test the ash of each embodiment and comparative example precursor product, broken filament intensity and extension at break, the results are shown in Table 5.
Table 1.
Table 2.
Table 3.
Table 4.
Table 5.
Claims (13)
1. a preparation method for polyacrylonitrile base carbon fiber precursors, spinning material polyacrylonitrile resin is the copolymer of three kinds of monomers, and the first monomer is acrylonitrile; Second comonomer takes from the one in methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate or vinylacetate; Third monomer is itaconic acid, and in polyacrylonitrile resin, the content of Third monomer is 0.5 ~ 2.0wt%, and second and the total content of Third monomer be 1.0 ~ 7.0wt%, it is characterized in that this preparation method comprises the following steps successively:
1) polyacrylonitrile resin with the NaSCN aqueous solution of 45 ~ 58wt% for solvent is mixed with spinning solution, with the NaSCN aqueous solution of 8 ~ 16wt% for coagulating bath adopt wet spinning technology through spray silk and solidification forming obtain as-spun fibre;
2) as-spun fibre carries out water-bath drawing-off in the NaSCN aqueous solution of 1 ~ 5wt%, and it is 5 ~ 30 DEG C that bath temperature controls, and it is 1.5 ~ 2.5 that drafting multiple controls;
3) as-spun fibre deionized water drip washing, it is 45 ~ 60 DEG C that water temperature controls, and drip washing time controling is 2 ~ 20min;
4) cushioning liquid that as-spun fibre is placed in containing sour A and salt B floods, A is sulfuric acid, hydrochloric acid or nitric acid, B is sodium salt or the sylvite of A, the pH value of cushioning liquid is 0.5 ~ 3.0, the concentration of sodium ion or potassium ion is 200 ~ 800mg/L, and the temperature of cushioning liquid controls to be 45 ~ 60 DEG C, with mass ratio range; bath raio controls as as-spun fibre: cushioning liquid=1: (15 ~ 25), and it is 2 ~ 15min that dip time controls;
5) as-spun fibre carries out water-bath drawing-off in pure water, and it is 95 ~ i00 DEG C that bath temperature controls, and it is 3 ~ 5 that drafting multiple controls;
6) as-spun fibre is placed in acidic aqueous solution and floods, acid adopts nitric acid, sulfuric acid or hydrochloric acid, the pH value of acidic aqueous solution is 3.0 ~ 5.0, it is 45 ~ 60 DEG C that temperature controls, with mass ratio range; bath raio controls as as-spun fibre: solution=1: (15 ~ 25), and it is 2 ~ 8min that dip time controls;
7) as-spun fibre temperature is that the deionized water of 90 ~ 100 DEG C carries out hot bath rinsing, until rinsing liquid is in neutral;
8) as-spun fibre makes polyacrylonitrile base carbon fiber precursors product through last handling process, and last handling process comprises and oiling and compacting by drying.
2. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that step 4) described in A be nitric acid, B is sodium nitrate.
3. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that step 4) described in the pH value of cushioning liquid be 1.0 ~ 2.0.
4. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that step 4) described in sodium ion or the concentration of potassium ion be 300 ~ 500mg/L.
5. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that step 4) described in the temperature of cushioning liquid be 45 ~ 55 DEG C.
6. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that step 4) described in bath raio control as as-spun fibre: cushioning liquid=1: (18 ~ 23).
7. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that step 4) described in dip time control be 4 ~ 8min.
8. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that step 6) described in the pH value of acidic aqueous solution be 3.5 ~ 4.5.
9. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that step 6) described in acidic aqueous solution temperature control be 50 ~ 55 DEG C.
10. the preparation method of polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that step 6) described in bath raio control as as-spun fibre: solution=1: (18 ~ 23).
The preparation method of 11. polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that step 6) described in dip time control be 3 ~ 5min.
The preparation method of 12. polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that the molecular weight of described polyacrylonitrile resin is 50000 ~ 200000.
The preparation method of 13. polyacrylonitrile base carbon fiber precursors according to claim 1, is characterized in that step 1) described in spinning solution in polyacrylonitrile resin content be 10 ~ 14wt%.
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