CN114437287A - Preparation method of polymer for polyacrylonitrile-based carbon fiber precursor without metal ions in polymerization system - Google Patents
Preparation method of polymer for polyacrylonitrile-based carbon fiber precursor without metal ions in polymerization system Download PDFInfo
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- CN114437287A CN114437287A CN202210313883.6A CN202210313883A CN114437287A CN 114437287 A CN114437287 A CN 114437287A CN 202210313883 A CN202210313883 A CN 202210313883A CN 114437287 A CN114437287 A CN 114437287A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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Abstract
A preparation method of a polymer for polyacrylonitrile-based carbon fiber protofilament without metal ions in a polymerization system comprises the steps of mixing monomer acrylonitrile, a second polymerization monomer, a third polymerization monomer and deionized water, heating and keeping the temperature at 45-65 ℃, stirring at 100rpm, then respectively dripping water-soluble initiators into a reactor at the same titration rate, and reacting for 30-120min after finishing dripping the initiators; removing residual monomers, washing and drying to obtain polyacrylonitrile powder; wherein, based on the mass of all the polymerization monomers, the monomer acrylonitrile accounts for 92-99 wt%, the feeding amount of the second comonomer accounts for 1-7.0 wt%, the feeding amount of the third comonomer accounts for 0.1-3.0 wt%, and the dosage of the initiator accounts for 0.1-2.0 wt%; in the initiator. The invention has the advantages of high polymerization reaction rate, low reaction temperature, high polymerization conversion rate and low production cost. Because the polymerization system does not contain metal ions, the polyacrylonitrile-based carbon fiber precursor with high purification and high quality can be obtained, and further the carbon fiber with high performance can be obtained.
Description
Technical Field
The invention relates to a preparation method of a polymer for polyacrylonitrile-based carbon fiber precursors, in particular to a preparation method of a polymer for polyacrylonitrile-based carbon fiber precursors, wherein a polymerization system does not contain metal ions.
Background
The carbon fiber is an excellent reinforced fiber material, and has the advantages of high strength, high modulus, high temperature resistance, wear resistance, corrosion resistance, fatigue resistance, creep resistance, small linear expansion coefficient, good electric conductivity, good heat conductivity and the like, so that the carbon fiber is widely applied to the fields of aerospace, marine transportation, rail transit vehicles, wind power blades, medical and industrial equipment, sports and leisure products and the like; with the continuous expansion of the application field, the strength requirement of the carbon fiber is continuously improved.
The preparation process of the high-performance polyacrylonitrile-based carbon fiber comprises the processes of monomer polymerization, precursor spinning, precursor stretching, precursor preoxidation, carbonization and the like; the high-quality polyacrylonitrile precursor is the premise of preparing the high-performance polyacrylonitrile carbon fiber. At present, polyacrylonitrile is mainly produced by a solution polymerization one-step method (homogeneous polymerization) and a water-phase precipitation polymerization two-step method (heterogeneous polymerization), wherein the solution polymerization is the most mature method in the synthesis industry, and the method has the advantages that the obtained polymer has low viscosity, is easy to mix, can be directly used for spinning after the reaction is finished, and the like; chinese patents CN101724922A, CN1167838C and CN101781809 adopt a one-step method to prepare polyacrylonitrile stock solution for carbon fibers by using dimethyl sulfoxide as a solvent. However, the polymerization degree of the polymer is small due to the high chain transfer coefficient of the solvent, the reaction time is long, and the solvent recovery after the reaction is difficult.
In view of zero chain transfer reaction constant of water, the Acrylonitrile (AN) polymer obtained by aqueous phase precipitation polymerization by using water as a reaction medium has higher average molecular weight, and meanwhile, the water as the reaction medium can realize that a reaction system has good heat exchange effect, and unreacted monomers are easy to recover. Meanwhile, the method usually adopts a water-soluble oxidation-reduction initiation system, and has the advantages of high polymerization reaction rate, low reaction temperature, narrow molecular weight distribution of the obtained product, high polymerization conversion rate and the like; chinese patents CN109721677A, CN104372431A and CN109721678A adopt a two-step method to prepare polyacrylonitrile spinning solution for carbon fibers by using an oxidation-reduction system initiator; however, the polymerization process of the two-step method generally adopts a redox system, and most of the polymerization process contains alkali metal ion impurities; when the protofilament is subjected to pre-oxidation and carbonization treatment,the existence of metal ion impurities can easily catalyze the oxidation of carbon to generate CO and CO2Gas is waited, so that a void defect is formed in the carbon fiber, and meanwhile, alkali metal impurities exist in the carbon fiber in the form of oxides, so that the performance of the carbon fiber is seriously influenced; therefore, the high purity of the precursor of the carbon fiber with excellent performance is also important; in the prior art, the impurities of metals can be removed on the surface of the protofilament fiber by means of washing, but the impurities from a polymerization initiation system are generally considered to be difficult to remove on a polymer molecular chain by a washing method, so that high-quality spinning solution is difficult to provide for preparing high-performance polyacrylonitrile carbon fiber.
Disclosure of Invention
The invention aims to provide a preparation method of a polymer for polyacrylonitrile-based carbon fiber precursors, which has a polymerization system without metal ions, and avoids metal impurities from a polymerization initiation system, and the obtained polymer for the polyacrylonitrile-based carbon fiber precursors has the advantages of high polymerization reaction rate, low reaction temperature, narrow polymer molecular weight distribution, high polymerization conversion rate, low production cost and the like in an aqueous precipitation polymerization method.
A preparation method of a polymer for polyacrylonitrile-based carbon fiber precursor without metal ions in a polymerization system comprises the following steps:
mixing a monomer acrylonitrile, a second polymerization monomer, a third polymerization monomer and deionized water, heating and keeping the temperature at 45-65 ℃, stirring at 100rpm, respectively dripping water-soluble initiators into the reactor at the same titration rate, and reacting for 30-120min after finishing dripping the initiators; removing residual monomers, washing and drying to obtain polyacrylonitrile powder; wherein, based on the mass of all the polymerization monomers, the monomer acrylonitrile accounts for 92-99 wt%, the feeding amount of the second comonomer accounts for 1-7.0 wt%, the feeding amount of the third comonomer accounts for 0.1-3.0 wt%, and the dosage of the initiator accounts for 0.1-2.0 wt%;
the initiator is a non-alkali metal redox initiation system and comprises an oxidant and a reducing agent.
In the initiator, the oxidant is ammonium chlorate; the reducing agent is one of ammonium bisulfite, ammonium sulfite, ammonium metabisulfite and ammonium metabisulfite;
in the initiator, the mass ratio of the oxidant to the reducing agent is 1-6: 1
The invention has the beneficial effects that:
compared with the prior art, the invention has the key that the initiating system in the aqueous precipitation polymerization adopts a water-soluble inorganic oxidation-reduction initiating system without alkali metal, and compared with the water-soluble inorganic oxidation-reduction initiating system containing metal ions, the invention keeps the advantages of high polymerization reaction rate, low reaction temperature, large polymer molecular weight, narrow molecular weight distribution, high polymerization conversion rate, low production cost and the like of the aqueous precipitation polymerization method, and greatly improves the purity of the polymer because the polymerization system does not contain any metal ions, thereby obtaining the polyacrylonitrile-based carbon fiber precursor with high purification and high quality and further obtaining the carbon fiber with high performance.
Detailed Description
A preparation method of a polymer for polyacrylonitrile-based carbon fiber precursor without metal ions in a polymerization system comprises the following specific embodiments:
example 1:
1) adding 960g of acrylonitrile, 20g of methyl acrylate, 20g of itaconic acid and 2000g of deionized water into a reactor at room temperature, stirring at the speed of 100rpm, heating to 50 ℃, keeping the temperature constant at the temperature for 0.5h, respectively adding an oxidant ammonium chlorate, a reducing agent ammonium bisulfite, and keeping the reaction at 50 ℃ for 1.5 h; filtering, removing the monomer and drying the polymer slurry to obtain white polyacrylonitrile powder; obtaining polyacrylonitrile with the weight-average molecular weight of 32.2 ten thousand and the molecular weight distribution index of 1.45;
2) mixing polyacrylonitrile powder with dimethylacetamide to prepare a spinning solution with a solid content of 20%, heating the spinning solution, spinning the spinning solution into a coagulating bath, carrying out negative drafting by 0.2%, carrying out total rinsing on the obtained nascent fiber by deionized water to remove a solvent, oiling at a drafting ratio of 9.98, and standing the oiled fiber at 150 ℃ for 4-5 minutes to carry out drying and densification to prepare polyacrylonitrile-based carbon fiber precursor; the strength of the obtained protofilament is 6.99 CN/dtex; after carbonization, the strength of the carbon fiber is 7.21 GPa.
Example 2:
1) adding 960g of acrylonitrile, 20g of methyl acrylate, 20g of itaconic acid and 2000g of deionized water into a reactor at room temperature, stirring at the speed of 100rpm, heating to 55 ℃, keeping the temperature constant at the temperature for 0.5h, respectively adding an oxidant ammonium chlorate, a reducing agent ammonium bisulfite, and keeping the reaction at 57 ℃ for 1 h; filtering, removing the monomer and drying the polymer slurry to obtain white polyacrylonitrile powder; obtaining polyacrylonitrile with the weight-average molecular weight of 39.6 ten thousand and the molecular weight distribution index of 1.60;
2) mixing polyacrylonitrile powder and dimethylacetamide to prepare a spinning solution with a solid content of 20%, heating the spinning solution, spinning the spinning solution into a coagulating bath, carrying out negative drafting by 0.2%, carrying out total rinsing on the obtained nascent fiber by deionized water to remove a solvent, oiling at a drafting ratio of 9.98, and allowing the oiled fiber to stay at 150 ℃ for 4-5 minutes to carry out drying and densification to prepare the polyacrylonitrile-based carbon fiber precursor. The strength of the obtained protofilament is 6.76 CN/dtex; after carbonization, the strength of the carbon fiber is 7.08 GPa.
Example 3:
1) adding 960g of acrylonitrile, 20g of methyl acrylate, 20g of itaconic acid and 2000g of deionized water into a reactor at room temperature, stirring at the speed of 100rpm, heating to 55 ℃, keeping the temperature constant for 0.5h, respectively adding an oxidant ammonium chlorate, a reducing agent ammonium sulfite, and keeping reacting for 1.5h at 55 ℃; filtering, removing the monomer and drying the polymer slurry to obtain white polyacrylonitrile powder; obtaining polyacrylonitrile with the weight-average molecular weight of 38.3 ten thousand and the molecular weight distribution index of 1.59;
2) mixing polyacrylonitrile powder and dimethylacetamide to prepare a spinning solution with the solid content of 20%, heating the spinning solution, spinning the spinning solution into a coagulating bath, carrying out negative drafting by 0.2%, carrying out total washing on the obtained nascent fiber by 0 deionized water to remove a solvent, oiling at a drafting ratio of 9.98, and standing the oiled fiber at 150 ℃ for 4-5 minutes to carry out drying and densification to prepare polyacrylonitrile-based carbon fiber precursor; the strength of the obtained protofilament is 7.02 CN/dtex. After carbonization, the strength of the carbon fiber is 7.19 GPa.
Example 4:
1) adding 960g of acrylonitrile, 20g of methyl acrylate, 20g of itaconic acid and 2000g of deionized water into a reactor at room temperature, stirring at the speed of 100rpm, heating to 55 ℃, keeping the temperature constant at the temperature for 0.5h, respectively adding ammonium chlorate serving as an oxidant and ammonium metabisulfite serving as a reducing agent, and keeping the reaction at the temperature of 55 ℃ for 2 h; filtering, removing the monomer and drying the polymer slurry to obtain white polyacrylonitrile powder; the weight average molecular weight of the polyacrylonitrile is 37.7 ten thousand, and the molecular weight distribution index is 1.49;
2) mixing polyacrylonitrile powder and dimethylacetamide to prepare a spinning stock solution with 20% of solid content, heating the spinning stock solution, spinning the spinning stock solution into a coagulating bath, carrying out negative drafting by 0.2%, carrying out total rinsing on the obtained nascent fiber by deionized water to remove a solvent, oiling at a drafting ratio of 9.98, and allowing the oiled fiber to stay at 150 ℃ for 4-5 minutes for drying and compacting to prepare polyacrylonitrile-based carbon fiber precursor; the strength of the obtained protofilament is 7.05 CN/dtex; after carbonization, the strength of the carbon fiber is 7.22 GPa.
Example 5:
1) adding 960g of acrylonitrile, 20g of methyl acrylate, 20g of itaconic acid and 2000g of deionized water into a reactor at room temperature, stirring at the speed of 100rpm, heating to 60 ℃, keeping the temperature constant at the temperature for 0.5h, adding ammonium chlorate serving as an oxidant and ammonium sulfite serving as a reducing agent respectively, and keeping the reaction at the temperature of 60 ℃ for 2 h; filtering, removing the monomer and drying the polymer slurry to obtain white polyacrylonitrile powder; the weight average molecular weight of the polyacrylonitrile is 36.8 ten thousand, and the molecular weight distribution index is 1.52;
2) mixing polyacrylonitrile powder and dimethylacetamide to prepare a spinning solution with the solid content of 20%, heating the spinning solution, spinning the spinning solution into a coagulating bath, carrying out negative drafting by 0.2%, carrying out total rinsing on the obtained nascent fiber by deionized water to remove a solvent, oiling at a drafting ratio of 9.98, and allowing the oiled fiber to stay at 150 ℃ for 4-5 minutes to carry out drying and densification to prepare polyacrylonitrile-based carbon fiber precursor; the strength of the obtained protofilament is 6.86 CN/dtex; after carbonization, the strength of the carbon fiber is 6.88 GPa.
Claims (3)
1. A preparation method of a polymer for polyacrylonitrile-based carbon fiber precursor without metal ions in a polymerization system is characterized by comprising the following steps: the method comprises the following steps:
mixing a monomer acrylonitrile, a second polymerization monomer, a third polymerization monomer and deionized water, heating and keeping the temperature at 45-65 ℃, stirring at 100rpm, respectively dripping water-soluble initiators into the reactor at the same titration rate, and reacting for 30-120min after finishing dripping the initiators; removing residual monomers, washing and drying to obtain polyacrylonitrile powder; wherein, based on the mass of all the polymerization monomers, the monomer acrylonitrile accounts for 92-99 wt%, the feeding amount of the second comonomer accounts for 1-7.0 wt%, the feeding amount of the third comonomer accounts for 0.1-3.0 wt%, and the dosage of the initiator accounts for 0.1-2.0 wt%;
the initiator is a non-alkali metal redox initiation system and comprises an oxidant and a reducing agent.
2. The method for preparing the polymer for the polyacrylonitrile-based carbon fiber precursor by the aqueous phase precipitation polymerization without the alkali metal redox initiation system according to claim 1, wherein the polymer is prepared by the following steps: in the initiator, the oxidant is ammonium chlorate; the reducing agent is one of ammonium bisulfite, ammonium sulfite, ammonium metabisulfite and ammonium metabisulfite.
3. The method for preparing the polymer for the polyacrylonitrile-based carbon fiber precursor by the aqueous phase precipitation polymerization without the alkali metal redox initiation system according to claim 2, wherein: in the initiator, the mass ratio of the oxidant to the reducing agent is 1-6: 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161694A (en) * | 2007-11-22 | 2008-04-16 | 吉林奇峰化纤股份有限公司 | Preparation method of polymer for polyacrylonitrile base carbon fiber precursors |
| CN108840974A (en) * | 2018-06-25 | 2018-11-20 | 长春工业大学 | A kind of preparation method of carbon fibre precursor ternary polyacrylonitrile copolymer |
| CN113336889A (en) * | 2021-06-24 | 2021-09-03 | 常州市宏发纵横新材料科技股份有限公司 | Preparation process and spinning process of high molecular weight polyacrylonitrile for preparing carbon fiber precursor |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161694A (en) * | 2007-11-22 | 2008-04-16 | 吉林奇峰化纤股份有限公司 | Preparation method of polymer for polyacrylonitrile base carbon fiber precursors |
| CN108840974A (en) * | 2018-06-25 | 2018-11-20 | 长春工业大学 | A kind of preparation method of carbon fibre precursor ternary polyacrylonitrile copolymer |
| CN113336889A (en) * | 2021-06-24 | 2021-09-03 | 常州市宏发纵横新材料科技股份有限公司 | Preparation process and spinning process of high molecular weight polyacrylonitrile for preparing carbon fiber precursor |
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