CN103614801A - Method for preparing high-crystallinity polyacrylonitrile nascent fiber - Google Patents
Method for preparing high-crystallinity polyacrylonitrile nascent fiber Download PDFInfo
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- CN103614801A CN103614801A CN201310642520.8A CN201310642520A CN103614801A CN 103614801 A CN103614801 A CN 103614801A CN 201310642520 A CN201310642520 A CN 201310642520A CN 103614801 A CN103614801 A CN 103614801A
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Abstract
The invention provides a method for preparing a high-crystallinity polyacrylonitrile nascent fiber and belongs to the technical field of carbon fiber precursors. The method comprises the following steps: ejecting an acrylonitrile polymer solution obtained by performing free radical polymerization on acrylonitrile and a comonomer through a spinneret orifice, performing coagulating phase separation in a coagulating bath, standing at normal temperature and drying at a constant temperature in a solution with the same composition as the coagulating bath; and taking a P value as a polarity index of the solution in the coagulating bath, regulating the composition of the coagulating bath, so that the polarity is in the range that an absolute value of (P-0.444) is more than 0.05 and less than 0.35, and the crystallinity of the prepared polyacrylonitrile nascent fiber is higher than 45 percent.
Description
[technical field]
The invention belongs to polyacrylonitrile fibre precursor technical field, be specifically related to a kind of method of preparing high-crystallinity polyacrylonitrile as-spun fibre.
[background technology]
The crystalline structure of polyacrylonitrile fibre precursor is a key factor that determines final carbon fiber performance.This is because precursor all has close relationship with crystalline structure in reaction process and the mechanism of follow-up pre-oxidation and carbonisation, finally affects structure and the performance of carbon fiber.Especially in the stabilization stage, the crystalline structure of precursor has determined the diffusion rate of oxygen at fibrous inside, the reaction process that has affected stabilization reaction, degree of crystallinity is high shows that fibre structure is more regular, is more conducive to the formation of the heat-resisting trapezium structure of stabilization process.Meanwhile, the exotherm of stabilization reaction is also closely related with the composition of crystalline structure.Heat release is too concentrated, or heat release is too fast or the excessively slow final performance for fiber has very large impact.Therefore the crystalline structure of polyacrylonitrile fibre precursor also or the height of degree of crystallinity plays conclusive effect for the performance of carbon fiber, and experience shows, the degree of crystallinity of polyacrylonitrile fibril and the degree of crystallinity of as-spun fibre are proportionate, and therefore want the degree of crystallinity that improves precursor to set about from improving as-spun fibre degree of crystallinity.All change coagulation bath temperature and coagulating bath concentration realize the method for regulation and control as-spun fibre degree of crystallinity mostly at present.Do not obtain a unified rule, not theoretical as supporting accurately yet.
[summary of the invention]
For overcoming in prior art as-spun fibre degree of crystallinity without the accurate defect of regulation and control theoretical foundation, the present invention is by regulating the polarity p value of coagulating bath solution composition to regulate and control the separated process of solidifying phase of polyacrylonitrile dynamic analysis of spinning, and then the formation of the crystalline structure of adjusting as-spun fibre, finally reach and improve polyacrylonitrile as-spun fibre degree of crystallinity.
For achieving the above object, the present invention is by the following technical solutions:
The invention provides a kind of method of preparing high-crystallinity polyacrylonitrile as-spun fibre, comprise the steps:
A) radical polymerization: at 50～60 ℃, in containing the dimethyl sulfoxide solvent of azodiisobutyronitrile, acrylonitrile and other comonomers carry out radical polymerization, obtain acrylonitrile polymer solution;
B) de-single deaeration, coagulation forming: after de-single deaeration, acrylonitrile polymer solution dynamic analysis of spinning is through spinnerets ejection, and coagulation forming obtains as-spun fibre in coagulating bath; Wherein the p value of coagulating bath is 0.0094<P<0.794;
C) dry: the as-spun fibre obtaining is put into and filled and coagulation bath composition same solution, after the standing 24h of normal temperature, take out fiber and put into constant temperature volatilization 12h at 70 ℃ of vacuum drying ovens and obtain as-spun fibre sample; As-spun fibre sample degree of crystallinity >=45% obtaining.
In preparation method provided by the invention, the P value of coagulating bath is: 0.05<|P-0.444|<0.35.
In preparation method provided by the invention, as-spun fibre sample degree of crystallinity >=45%.
In preparation method provided by the invention, acrylonitrile can carry out radical polymerization with comonomer, comonomer is itaconic acid, methyl acrylate, methyl methacrylate, methacrylic acid, acrylamides etc. do not have in the molecule of strong polar group any one or 2 kinds and any combination of more than two kinds, obtain the mass fraction of acrylonitrile in acrylonitrile polymer solution higher than 95%.
In preparation method provided by the invention, coagulating bath be pure reagent or mixed solution, pure reagent is ethylene glycol, anhydrous acetic acid, ethanol, acetone, ethyl acetate; Mix reagent is water, dimethyl sulfoxide (DMSO), ethanol, acetone, acetic acid, any 2 kinds or above mixed liquor in ethyl acetate.
In the present invention, adopted P as a physical quantity that represents coagulating bath solution polarity, the polarity of mixed solution can be passed through empirical equation P=P
1* V
1+ P
2* V
2, P wherein
1and V
1represent respectively a kind of polarity of reagent and volume fraction (in the present invention, the polarity number P of reagent is usingd the polarity of water as the relative polarity of standard value 1), P
2and V
2represent polarity and the volume fraction of another kind of reagent.Can there is solidifying phase separation process in the spinning solution thread that enters coagulating bath, dimethyl sulfoxide (DMSO) in thread removes gradually under concentration difference effect, and precipitating agent in coagulating bath solution part will enter in the middle of thread, along with the carrying out being separated, as-spun fibre forms gradually.Step 2 in the present invention) and in step 3), immerse 2 coagulating baths, due to step 2) inconsistent according to different experimental conditions setting time, the immersion again of step 3) is fully solidified it, guarantees that the error that setting time difference causes result is enough little.The component of solution step 2) and coagulating bath in step 3) is identical, and both P values are identical.
As-spun fibre is carried out to XRD scanning, utilize degree of crystallinity formula degree of crystallinity=Ac/ (Ac+Aa) * 100% can obtain the degree of crystallinity of as-spun fibre.
The present invention adopts P value as the parameter of coagulating bath solution polarity in as-spun fibre preparation process, the P value of usining regulates and controls the component of coagulating bath as standard, control the polarity of coagulating bath solution within the specific limits, finally solidify and obtain degree of crystallinity at more than 45% as-spun fibre.
Effect of the present invention: using p value as the parameter of weighing coagulating bath solution polarity.By changing coagulating bath component, regulate and control P value, make P value within the scope of 0.05<|P-0.444|<0.35, solidify the degree of crystallinity of the polyacrylonitrile as-spun fibre obtaining more than 45%.By examples prove, any pure reagent or mixed solution be available above-mentioned standard allotment coagulation bath composition all.
[specific embodiment]
Embodiment 1
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), makees solvent, and azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtains acrylonitrile itaconic acid bipolymer, and comonomer ratio is 99:1.Through 12h, de-single deaeration can be carried out spinning.Coagulating bath is ethylene glycol, and measuring pump pump is 1.5ml/r for amount, and dynamic analysis of spinning, through spinnerets ejection, enters coagulation forming in coagulating bath, and setting time is 8 seconds, and coagulating bath drawing-off is-10%, and temperature is room temperature.The as-spun fibre obtaining is put into the wide-mouth bottle filling with coagulation bath composition same solution, takes out fiber and put into constant temperature volatilization 12h at 70 ℃ of vacuum drying ovens after the standing 24h of normal temperature.Dry fiber is cut into Powdered, the X`Pert PRO type X-ray diffractometer that adopts Dutch PANalytical company to produce is tested powder, sweep interval is 5 °～50 °, sweep speed is 0.089 °/s, obtain the XRD curve of polyacrylonitrile fibre, utilize the swarming software in JADE software to carry out swarming matching to curve, utilize the computing formula of degree of crystallinity: degree of crystallinity=Ac/ (Ac+Aa) * 100% can try to achieve the degree of crystallinity of fiber, in formula, Ac represents near the peak crystallization area 2 θ=17 °, and Aa represents the area at unformed peak.
Embodiment 2
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), makees solvent, and azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtains acrylonitrile itaconic acid bipolymer, and comonomer ratio is 99:1, and polymerization technique is with embodiment 1.Coagulating bath is anhydrous acetic acid, and all the other technological parameters and step are with embodiment 1.
Embodiment 3
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), makees solvent, and azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtains acrylonitrile itaconic acid bipolymer, and comonomer ratio is 99:1, and polymerization technique is with embodiment 1.Coagulating bath is ethanol, and all the other technological parameters and step are with embodiment 1.
Embodiment 4
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), makees solvent, and azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtains acrylonitrile itaconic acid bipolymer, and comonomer ratio is 99:1, and polymerization technique is with embodiment 1.Coagulating bath is acetone, and all the other technological parameters and step are with embodiment 1.
Embodiment 5
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), makees solvent, and azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtains acrylonitrile itaconic acid bipolymer, and comonomer ratio is 99:1, and polymerization technique is with embodiment 1.Coagulating bath is ethyl acetate, and all the other technological parameters and step are with embodiment 1.
Embodiment 6
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), makees solvent, and azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtains acrylonitrile itaconic acid bipolymer, and comonomer ratio is 99:1, and polymerization technique is with embodiment 1.Coagulating bath is the mixture of water and dimethyl sulfoxide (DMSO), and wherein the volume ratio of water and dimethyl sulfoxide (DMSO) is 1:1, and all the other technological parameters and step are with embodiment 1.
Embodiment 7
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), makees solvent, and azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtains acrylonitrile itaconic acid bipolymer, and comonomer ratio is 99:1, and polymerization technique is with embodiment 1.Coagulating bath is the mixture of water and dimethyl sulfoxide (DMSO), and wherein the volume ratio of water and dimethyl sulfoxide (DMSO) is 1:2, and all the other technological parameters and step are with embodiment 2.
Embodiment 8
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), makees solvent, and azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtains acrylonitrile itaconic acid bipolymer, and comonomer ratio is 99:1, and polymerization technique is with embodiment 1.Coagulating bath is the mixture of water and dimethyl sulfoxide (DMSO), and wherein the volume ratio of water and dimethyl sulfoxide (DMSO) is 1:3, and all the other technological parameters and step are with embodiment 3.
Embodiment 9
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), makees solvent, and azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtains acrylonitrile itaconic acid bipolymer, and comonomer ratio is 99:1, and polymerization technique is with embodiment 1.Coagulating bath is the mixture of water and dimethyl sulfoxide (DMSO), and wherein the volume ratio of water and dimethyl sulfoxide (DMSO) is 1:4, and all the other technological parameters and step are with embodiment 4.
Embodiment 10
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid bipolymer, comonomer ratio is 98:2, coagulating bath is water and dimethyl sulfoxide (DMSO) mixture, and wherein the volume ratio of water and dimethyl sulfoxide (DMSO) is 1:2, and all the other technological parameters and step are with embodiment 7.
Embodiment 11
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid bipolymer, comonomer ratio is 98:2, coagulating bath is water and alcohol mixture, and wherein the volume ratio of water and ethanol is 1:2, and all the other technological parameters and step are with embodiment 10.
Embodiment 12
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid bipolymer, comonomer ratio is 98:2, coagulating bath is water and acetone mixture, and wherein the volume ratio of water and acetone is 1:2, and all the other technological parameters and step are with embodiment 10.
Embodiment 13
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid bipolymer, comonomer ratio is 98:2, coagulating bath is water and acetate mixture, and wherein the volume ratio of water and acetic acid is 1:2, and all the other technological parameters and step are with embodiment 10.
Embodiment 14
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid bipolymer, comonomer ratio is 98:2, coagulating bath is ethanol and acetate mixture, and wherein the volume ratio of ethanol and acetic acid is 1:2, and all the other technological parameters and step are with embodiment 10.
Embodiment 15
Take acrylonitrile, itaconic acid is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid bipolymer, comonomer ratio is 98:2, coagulating bath is acetone and ethyl acetate mixture, and wherein the volume ratio of acetoneand ethyl acetate is 1:2, and all the other technological parameters and step are with embodiment 10.
Embodiment 16
Take acrylonitrile, itaconic acid, methyl acrylate is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid-methyl acrylate terpolymer, comonomer ratio is 98:1:1, coagulating bath is water and ethanol, and wherein the volume ratio of water and ethanol is 1:2, and all the other technological parameters and step are with embodiment 11.
Embodiment 17
Take acrylonitrile, itaconic acid, methyl acrylate is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid-methyl acrylate terpolymer, comonomer ratio is 98:1:1, coagulating bath is water, ethanol and acetic acid, and wherein the volume ratio of water and ethanol, acetic acid is 1:1:1, and all the other technological parameters and step are with embodiment 16.
Embodiment 18
Take acrylonitrile, itaconic acid, methyl acrylate is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid-methyl acrylate terpolymer, comonomer ratio is 98:1:1, coagulating bath is water, ethanol and dimethyl sulfoxide (DMSO), and wherein the volume ratio of water and ethanol, dimethyl sulfoxide (DMSO) is 1:1:1, and all the other technological parameters and step are with embodiment 16.
Embodiment 19
Take acrylonitrile, itaconic acid, methyl acrylate is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid-methyl acrylate terpolymer, comonomer ratio is 98:1:1, coagulating bath is water, ethanol and acetone, and wherein the volume ratio of water and ethanol, acetone is 1:1:1, and all the other technological parameters and step are with embodiment 16.
Embodiment 20
Take acrylonitrile, itaconic acid, methyl acrylate is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid-methyl acrylate terpolymer, comonomer ratio is 98:1:1, coagulating bath is water, ethanol and ethyl acetate, and wherein the volume ratio of water and ethanol, ethyl acetate is 1:1:1, and all the other technological parameters and step are with embodiment 16.
Embodiment 21
Take acrylonitrile, itaconic acid, methyl acrylate is comonomer, with dimethyl sulfoxide (DMSO), make solvent, azodiisobutyronitrile is that initator carries out radical polymerization at 60 ℃, obtain acrylonitrile itaconic acid-methyl acrylate terpolymer, comonomer ratio is 98:1:1, coagulating bath is dimethyl sulfoxide (DMSO), acetoneand ethyl acetate, and wherein the volume ratio of dimethyl sulfoxide (DMSO) and acetone, ethyl acetate is 1:1:1, and all the other technological parameters and step are with embodiment 16.
By the polarity P of coagulating bath solution in above-described embodiment, and the degree of crystallinity of corresponding as-spun fibre is listed in table 1.
Table 1 as-spun fibre degree of crystallinity
| Embodiment | Coagulating bath polarity P | As-spun fibre degree of crystallinity |
| 1 | 0.79 | 45.27% |
| 2 | 0.654 | 48.85% |
| 3 | 0.648 | 47.58% |
| 4 | 0.355 | 52.64% |
| 5 | 0.228 | 50.33% |
| 6 | 0.722 | 47.33% |
| 7 | 0.629 | 49.12% |
| 8 | 0.583 | 48.86% |
| 9 | 0.555 | 50.25% |
| 10 | 0.629 | 50.78% |
| 11 | 0.769 | 49.63% |
| 12 | 0.57 | 48.94% |
| 13 | 0.765 | 47.17% |
| 14 | 0.65 | 50.23% |
| 15 | 0.27 | 51.99% |
| 16 | 0.769 | 53.09% |
| 17 | 0.767 | 48.40% |
| 18 | 0.699 | 48.74% |
| 19 | 0.670 | 47.98% |
| 20 | 0.627 | 45.89% |
| 21 | 0.342 | 48.37% |
Claims (8)
1. a method of preparing high-crystallinity polyacrylonitrile as-spun fibre, comprises the steps:
A) radical polymerization: at 50～60 ℃, in containing the dimethyl sulfoxide solvent of azodiisobutyronitrile, acrylonitrile and other comonomers carry out radical polymerization, obtain acrylonitrile polymer solution;
B) de-single deaeration, coagulation forming: after de-single deaeration, acrylonitrile polymer solution dynamic analysis of spinning is through spinnerets ejection, and coagulation forming obtains as-spun fibre in coagulating bath;
The p value of described coagulating bath is 0.0094<P<0.794;
C) dry: the as-spun fibre obtaining is put into and filled and coagulation bath composition same solution, after the standing 24h of normal temperature, take out fiber and put into constant temperature volatilization 12h at 70 ℃ of vacuum drying ovens and obtain as-spun fibre sample;
Described as-spun fibre sample degree of crystallinity >=45%.
2. preparation method according to claim 1, is characterized in that: described P value is: 0.05<|P-0.444|<0.35.
3. preparation method according to claim 2, is characterized in that: described as-spun fibre sample degree of crystallinity >=45%.
4. preparation method according to claim 1, is characterized in that: described comonomer is itaconic acid, methyl acrylate, methyl methacrylate, methacrylic acid, any one or 2 kinds and any combination of more than two kinds in acrylamide.
5. preparation method according to claim 4, is characterized in that, in described acrylonitrile polymer solution, the mass fraction of acrylonitrile is higher than 95%.
6. preparation method according to claim 1, is characterized in that: described coagulating bath be pure reagent or mixed solution.
7. preparation method according to claim 6, is characterized in that: the pure reagent of described coagulating bath is ethylene glycol, anhydrous acetic acid, ethanol, acetone, ethyl acetate.
8. preparation method according to claim 7, is characterized in that: the mix reagent of described coagulating bath is water, dimethyl sulfoxide (DMSO), ethanol, acetone, acetic acid, any 2 kinds or above mixed liquor in ethyl acetate.
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Cited By (5)
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|---|---|---|---|---|
| CN104894674A (en) * | 2015-06-18 | 2015-09-09 | 国网智能电网研究院 | Method for improving crystallinity of polyacrylonitrile nascent fibers |
| CN109023594A (en) * | 2018-08-09 | 2018-12-18 | 北京化工大学 | Superhigh intensity, polyacrylonitrile carbon fiber of middle high-modulus attribute and preparation method thereof |
| CN111304768A (en) * | 2020-04-15 | 2020-06-19 | 北京化工大学 | High-crystallinity polyacrylonitrile nascent fiber and preparation method thereof |
| CN115341308A (en) * | 2022-09-01 | 2022-11-15 | 安徽大学 | Continuous production method for preparing polyacrylonitrile spinning solution by X-ray irradiation |
| CN116288772A (en) * | 2023-03-13 | 2023-06-23 | 山东大学 | Solidification forming method for improving homogenization and crystallinity of polyacrylonitrile nascent fiber |
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| CN102260919A (en) * | 2011-06-29 | 2011-11-30 | 中国科学院宁波材料技术与工程研究所 | Method for homogenizing, solidifying and forming polyacrylonitrile precursor |
| CN102586921A (en) * | 2011-01-06 | 2012-07-18 | 北京腾化技术有限责任公司 | Method for producing polyacrylonitrile-based carbon fiber precursor |
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| CN101643943A (en) * | 2009-07-10 | 2010-02-10 | 东华大学 | Preparation method for polyacrylonitrile-based carbon fiber protofilament |
| CN102586921A (en) * | 2011-01-06 | 2012-07-18 | 北京腾化技术有限责任公司 | Method for producing polyacrylonitrile-based carbon fiber precursor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104894674A (en) * | 2015-06-18 | 2015-09-09 | 国网智能电网研究院 | Method for improving crystallinity of polyacrylonitrile nascent fibers |
| CN109023594A (en) * | 2018-08-09 | 2018-12-18 | 北京化工大学 | Superhigh intensity, polyacrylonitrile carbon fiber of middle high-modulus attribute and preparation method thereof |
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| CN111304768A (en) * | 2020-04-15 | 2020-06-19 | 北京化工大学 | High-crystallinity polyacrylonitrile nascent fiber and preparation method thereof |
| CN115341308A (en) * | 2022-09-01 | 2022-11-15 | 安徽大学 | Continuous production method for preparing polyacrylonitrile spinning solution by X-ray irradiation |
| CN116288772A (en) * | 2023-03-13 | 2023-06-23 | 山东大学 | Solidification forming method for improving homogenization and crystallinity of polyacrylonitrile nascent fiber |
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