CN115233339A - Preparation method of high-hydrophilicity polyacrylonitrile spinning solution - Google Patents
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- CN115233339A CN115233339A CN202210810206.5A CN202210810206A CN115233339A CN 115233339 A CN115233339 A CN 115233339A CN 202210810206 A CN202210810206 A CN 202210810206A CN 115233339 A CN115233339 A CN 115233339A
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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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- 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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Abstract
The invention relates to a preparation method of a polyacrylonitrile spinning solution with high hydrophilicity. The method comprises the following steps: and (3) carrying out copolymerization reaction on the acrylonitrile monomer, the second comonomer, the third comonomer, the initiator and the solvent to obtain a polymerization solution, and removing the monomer and the defoaming to obtain the acrylonitrile-butadiene-styrene copolymer. The method has the advantages of low cost, easy control of reaction, uniform chain structure of the prepared polymer and good hydrophilicity.
Description
Technical Field
The invention belongs to the field of carbon fibers, and particularly relates to a preparation method of a polyacrylonitrile spinning solution with high hydrophilicity.
Background
The carbon fiber is a fibrous carbon material with the carbon element content accounting for more than 90 percent of the total mass, has the characteristics of high strength and high modulus, low density, corrosion resistance, good electric and thermal conductivity, good creep resistance and the like, and also has the soft processing performance of textile fiber, thereby becoming the main variety of special fiber. Carbon fibers have become the mainstream reinforcing fibers in composite materials because of their excellent properties such as high specific strength, high specific modulus, and fatigue resistance. In recent years, with the rapid development of the wind power field, the application demand of carbon fiber on the wind power blade thereof also rises rapidly. Secondly, the high-performance carbon fiber composite material is used as a light and high-strength structural material and is widely applied to the aerospace field. In addition, in recent years, various enterprises in China continuously invest in large-tow carbon fiber projects, the requirement of the carbon fiber composite material in the civil field is influenced to be increased continuously, and the carbon fiber composite material is more widely applied to the aspects of automobile high-speed rails, sports and leisure articles, major engineering and the like.
At present, problems in the preparation process of carbon fibers in China limit the development of carbon fibers in China to high performance and low cost, and one important problem is how to improve the quality of precursor fibers. The high-quality spinning solution is the basis for preparing polyacrylonitrile protofilament, and the quality of the protofilament can be improved by properly improving the hydrophilicity of the spinning solution. The improvement of the hydrophilicity of the polyacrylonitrile spinning solution is beneficial to controlling the solidification forming process of the nascent fiber, slowing down the double diffusion in the solidification bath and reducing the formation of holes in the nascent fiber, thereby obtaining the high-performance protofilament with uniform structure, high compactness and few defects. In addition, after the hydrophilicity of the polyacrylonitrile precursor is improved, in the subsequent high-pressure steam drafting stage, the precursor and water vapor can be better infiltrated and combined, water molecules penetrate into the fiber to play a plasticizing role, the drafting of the precursor is promoted, the orientation degree of the precursor is favorably improved, the defects of the precursor are reduced, and meanwhile, the introduction of other impurities is prevented, so that the high-performance carbon fiber precursor is obtained, and the foundation is laid for preparing the high-performance carbon fiber.
Chinese patent CN101148489A (published as 2008/3/26) discloses a hydrophilic spinning solution for polyacrylonitrile-based carbon fibers and a preparation method thereof, in the method, vinyl imidazolium salt, acrylonitrile, itaconic acid and other monomers are copolymerized to prepare a high-hydrophilicity polyacrylonitrile-based spinning stock solution containing a vinyl imidazolium salt structural unit, but since the vinyl imidazolium salt belongs to ionic liquid, the production cost is high, and the subsequent large-scale industrial production is not facilitated.
Chinese patent CN102733011B (published 2015, 5/6) discloses a method for preparing polyacrylonitrile spinning solution, which comprises preparing a polyacrylonitrile copolymer containing carboxylic acids, and then introducing ammonia gas into the polymerization solution to convert part of carboxyl groups in the copolymer into ammonium salts. Although the method can effectively improve the hydrophilicity of polyacrylonitrile, the reaction of ammonia gas and polyacrylonitrile stock solution with high viscosity is a complex heterogeneous reaction, the mass transfer is difficult and the reaction is not easy to control.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a polyacrylonitrile spinning solution with high hydrophilicity, so as to overcome the defect of poor hydrophilicity of polyacrylonitrile copolymer in the prior art.
The invention provides a preparation method of a high-hydrophilicity polyacrylonitrile spinning solution, which comprises the following steps:
carrying out copolymerization reaction on an acrylonitrile monomer, a second comonomer, a third comonomer, an initiator and a solvent to obtain a polymerization solution, and carrying out demonomerization and defoaming to obtain the high-hydrophilicity polyacrylonitrile spinning solution, wherein the second comonomer comprises itaconic acid, itaconic anhydride, acrylic acid, methacrylic acid or crotonic acid, and the third comonomer is (1-amino-2-propenyl) phosphonic acid, (Z) -3-amino-2-phosphonoxypropyl-2-olefine acid, (Z) -2-amino-5-phosphonopent-3-olefine acid, 1-amino-3- (phosphonomethylidene) cyclobutane-1-carboxylic acid, 1-amino-3-phosphono-2-cyclopentene-1-carboxylic acid or 1-amino-3-phosphono-3-cyclopentene-1-carboxylic acid.
Preferably, the second comonomer comprises itaconic acid, acrylic acid or methacrylic acid.
Preferably, the initiator comprises azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, or ammonium persulfate; more preferably, the initiator is azobisisobutyronitrile.
Preferably, the solvent comprises dimethyl sulfoxide, dimethylformamide or dimethylacetamide; more preferably, the solvent is dimethyl sulfoxide.
Preferably, the copolymerization reaction has the following process parameters: the copolymerization reaction temperature is 50-70 ℃ under the nitrogen atmosphere, and the copolymerization reaction time is 8-30 hours.
Preferably, the acrylonitrile monomer accounts for 90 to 99.5 percent of the total mass of the acrylonitrile monomer, the second comonomer and the third comonomer; the mass ratio of the second comonomer to the third comonomer is 1-9:9-1; the mass of the initiator is 0.3-0.5% of the total mass of the acrylonitrile monomer, the second comonomer and the third comonomer; the total mass of the acrylonitrile monomer, the second comonomer and the third comonomer accounts for 20-30% of the mass of the reaction system.
Preferably, the demonomerization process comprises the following steps: the polymerization solution was distilled under vacuum, and the residual monomer content was controlled to 0.1% or less.
Preferably, the defoaming pressure is 5-20 KPa, the defoaming temperature is 20-80 ℃, and the defoaming time is 1-6 days.
Preferably, the viscosity average molecular weight of the polyacrylonitrile copolymer in the high-hydrophilicity polyacrylonitrile spinning solution is 10-40 ten thousand, the molecular weight distribution is 1-6, and the solid content is 18-25%.
The invention also provides the high-hydrophilicity polyacrylonitrile spinning solution prepared by the preparation method.
The invention also provides application of the high-hydrophilicity polyacrylonitrile spinning solution prepared by the preparation method in spinning.
On the basis of binary copolymerization of acrylonitrile and common carboxylic acid monomers, the high-hydrophilicity polyacrylonitrile-based carbon fiber spinning solution is prepared by introducing phosphate groups and amino groups, and has the advantages of low cost, easy reaction control, good hydrophilicity and the like.
Advantageous effects
(1) The carboxyl in the carboxylic acid monomer can weaken the dipolar interaction force in cyano-group molecules and among molecules in PAN molecules, and when fibers are subjected to pre-oxidation treatment, the carboxyl initiates cyclization reaction of the fibers by an anion mechanism, so that the cyclization reaction temperature of the polyacrylonitrile fibers is reduced, the phenomenon of severe heat release is avoided, and the uniformity and compactness of the fibers are improved;
(2) The third comonomer used in the invention has hydrophilic phosphonic acid group and amino group at the same time, the introduction of phosphonic acid group and amino group into the molecular structure of hydrophobic PAN can obviously improve the hydrophilicity, and can promote the fine structure of the precipitated structure of the coagulated fiber during spinning, and promote the reduction of the pore structure of the nascent fiber, thereby being beneficial to improving the performance of the subsequent carbon fiber;
(3) The invention has good hydrophilicity, the contact angle of the spinning solution after film formation with water is 40-55 degrees, the cost is low, the reaction is easy to control, and the invention is suitable for preparing the multifunctional polyacrylonitrile-based carbon fiber protofilament.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
(1) Carrying out solution copolymerization reaction on a reaction system comprising acrylonitrile, itaconic acid, (1-amino-2-propenyl) phosphonic acid, azodiisobutyronitrile and dimethyl sulfoxide at 60 ℃ in a nitrogen atmosphere, and reacting for 15 hours to obtain a polymerization solution. The mass ratio of acrylonitrile/itaconic acid/(1-amino-2-propenyl) phosphonic acid is 97.0/1.0/2.0, the mass concentration of the total monomer is 25%, and the dosage of the azodiisobutyronitrile is 0.3% of the total weight of the monomers.
(2) Distilling the polymerization solution obtained in the step (1) under a vacuum condition to remove monomers, wherein the content of residual monomers is controlled to be below 0.1%;
(3) And (3) defoaming the spinning solution obtained in the step (2), wherein the defoaming treatment pressure is 15KPa, the defoaming treatment temperature is 60 ℃, and the defoaming treatment time is 4 days, so as to obtain the high-hydrophilicity polyacrylonitrile spinning solution.
Through testing, the viscosity average molecular weight of the copolymer is 21 ten thousand, the molecular weight distribution is 2.5, the solid content of the spinning solution is 19%, the stock solution is uniformly coated on the surface of glass to form a flat film with the thickness of 2mm, then a contact angle measuring instrument is used for dropping deionized water on the surface for testing, and the contact angle is 47.2 degrees.
Example 2
(1) Carrying out solution copolymerization reaction on a reaction system comprising acrylonitrile, itaconic acid, 1-amino-3-phosphono-2-cyclopentene-1-carboxylic acid, azobisisobutyronitrile and dimethyl sulfoxide at 60 ℃ in a nitrogen atmosphere, and reacting for 15 hours to obtain a polymerization solution. The mass ratio of acrylonitrile/itaconic acid/1-amino-3-phosphono-2-cyclopentene-1-carboxylic acid is 99.50/0.45/0.05, the mass concentration of the total monomer is 25%, and the dosage of the azodiisobutyronitrile is 0.3% of the total weight of the monomers.
(2) Distilling the polymerization solution obtained in the step (1) under a vacuum condition to remove monomers, wherein the content of residual monomers is controlled to be below 0.1%;
(3) And (3) defoaming the spinning solution obtained in the step (2), wherein the defoaming treatment pressure is 15KPa, the defoaming treatment temperature is 60 ℃, and the defoaming treatment time is 4 days, so as to obtain the high-hydrophilicity polyacrylonitrile spinning solution.
Through testing, the viscosity average molecular weight of the copolymer is 33 ten thousand, the molecular weight distribution is 2.6, the solid content of the spinning solution is 21%, the stock solution is uniformly coated on the surface of glass to form a smooth film with the thickness of 2mm, then a contact angle measuring instrument is used for dropping deionized water on the surface for testing, and the contact angle is 54.7 degrees.
Example 3
(1) Carrying out solution copolymerization reaction on a reaction system comprising acrylonitrile, acrylic acid, (Z) -2-amino-5-phosphonopent-3-enoic acid, azobisisobutyronitrile and dimethyl sulfoxide at 55 ℃ in a nitrogen atmosphere, and reacting for 12 hours to obtain a polymerization solution. The mass ratio of acrylonitrile/acrylic acid/(Z) -2-amino-5-phosphono-pent-3-enoic acid is 96.0/2.0/2.0, the mass concentration of the total monomer is 25%, and the dosage of the azodiisobutyronitrile is 0.3% of the total weight of the monomers.
(2) Distilling the polymerization solution obtained in the step (1) under a vacuum condition to remove monomers, wherein the content of residual monomers is controlled to be below 0.1%;
(3) And (3) defoaming the spinning solution obtained in the step (2), wherein the defoaming treatment pressure is 12KPa, the defoaming treatment temperature is 55 ℃, and the defoaming treatment time is 3 days, so as to obtain the high-hydrophilicity polyacrylonitrile spinning solution.
Through testing, the viscosity average molecular weight of the copolymer is 21 ten thousand, the molecular weight distribution is 2.3, the solid content of the spinning solution is 18%, the stock solution is uniformly coated on the surface of glass to form a smooth film with the thickness of 2mm, then deionized water is dripped on the surface by a contact angle measuring instrument for testing, and the contact angle is 46.9 degrees.
Example 4
(1) Carrying out solution copolymerization reaction on a reaction system comprising acrylonitrile, acrylic acid, 1-amino-3-phosphono-3-cyclopentene-1-carboxylic acid, azobisisobutyronitrile and dimethyl sulfoxide at 55 ℃ in a nitrogen atmosphere, and reacting for 12 hours to obtain a polymerization solution. The mass ratio of acrylonitrile/acrylic acid/1-amino-3-phosphonyl-3-cyclopentene-1-carboxylic acid is 98.0/1.5/0.5, the mass concentration of the total monomer is 25%, and the dosage of azodiisobutyronitrile is 0.3% of the total weight of the monomers.
(2) Distilling the polymerization solution obtained in the step (1) under a vacuum condition to remove monomers, wherein the content of residual monomers is controlled to be below 0.1%;
(3) And (3) defoaming the spinning solution obtained in the step (2), wherein the defoaming treatment pressure is 12KPa, the defoaming treatment temperature is 55 ℃, and the defoaming treatment time is 3 days, so as to obtain the high-hydrophilicity polyacrylonitrile spinning solution.
Through testing, the viscosity average molecular weight of the copolymer is 29 ten thousand, the molecular weight distribution is 2.5, the solid content of the spinning solution is 20%, the stock solution is uniformly coated on the surface of glass to form a smooth film with the thickness of 2mm, then a contact angle measuring instrument is used for dropping deionized water on the surface for testing, and the contact angle is 53.2 degrees.
Comparative example 1
(1) And (2) carrying out solution copolymerization reaction on a reaction system comprising acrylonitrile, itaconic acid, azodiisobutyronitrile and dimethyl sulfoxide at 55 ℃ in a nitrogen atmosphere, and reacting for 15 hours to obtain a polymerization solution. The mass ratio of acrylonitrile to itaconic acid is 98.0/2.0, the mass concentration of the total monomer is 25%, and the dosage of the azodiisobutyronitrile is 0.3% of the total weight of the monomers.
(2) Distilling the polymerization solution obtained in the step (1) under a vacuum condition to remove monomers, wherein the content of residual monomers is controlled to be below 0.1%;
(3) And (3) defoaming the spinning solution obtained in the step (2), wherein the defoaming treatment pressure is 12KPa, the defoaming treatment temperature is 55 ℃, and the defoaming treatment time is 3 days to obtain the polyacrylonitrile spinning solution.
Through testing, the viscosity average molecular weight of the copolymer is 26 ten thousand, the molecular weight distribution is 2.7, the solid content of the spinning solution is 19%, the stock solution is uniformly coated on the surface of glass to form a smooth film with the thickness of 2mm, then a contact angle measuring instrument is used for dropping deionized water on the surface for testing, the contact angle is measured to be 65.9 degrees, and the hydrophilicity is poor.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to limit the present invention in any way, and any person skilled in the art may make variations or modifications to the equivalent embodiments using the technical content disclosed above. However, any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a polyacrylonitrile spinning solution with high hydrophilicity comprises the following steps:
carrying out copolymerization reaction on an acrylonitrile monomer, a second comonomer, a third comonomer, an initiator and a solvent to obtain a polymerization solution, and carrying out demonomerization and defoaming to obtain the high-hydrophilicity polyacrylonitrile spinning solution, wherein the second comonomer comprises itaconic acid, itaconic anhydride, acrylic acid, methacrylic acid or crotonic acid, and the third comonomer comprises (1-amino-2-propenyl) phosphonic acid, (Z) -3-amino-2-phosphonoxypropyl-2-olefine acid, (Z) -2-amino-5-phosphonopent-3-olefine acid, 1-amino-3- (phosphonomethylidene) cyclobutane-1-carboxylic acid, 1-amino-3-phosphono-2-cyclopentene-1-carboxylic acid or 1-amino-3-phosphono-3-cyclopentene-1-carboxylic acid.
2. The method of claim 1, wherein the initiator comprises azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, or ammonium persulfate.
3. The method of claim 1, wherein the solvent comprises dimethyl sulfoxide, dimethylformamide, or dimethylacetamide.
4. The preparation method according to claim 1, wherein the copolymerization reaction has the following process parameters: the copolymerization reaction temperature is 50-70 ℃ under the nitrogen atmosphere, and the copolymerization reaction time is 8-30 hours.
5. The method according to claim 1, wherein the acrylonitrile monomer is 90 to 99.5% by mass of the total mass of the acrylonitrile monomer, the second comonomer and the third comonomer; the mass ratio of the second comonomer to the third comonomer is 1-9:9-1; the mass of the initiator is 0.3-0.5% of the total mass of the acrylonitrile monomer, the second comonomer and the third comonomer; the total mass of the acrylonitrile monomer, the second comonomer and the third comonomer accounts for 20-30% of the mass of the reaction system.
6. The preparation method according to claim 1, wherein the demonomerization process is: the polymerization solution was distilled under vacuum, and the residual monomer content was controlled to 0.1% or less.
7. The process according to claim 1, wherein the defoaming pressure is 5 to 20KPa, the defoaming temperature is 20 to 80 ℃, and the defoaming time is 1 to 6 days.
8. The preparation method according to claim 1, wherein the polyacrylonitrile copolymer in the polyacrylonitrile spinning solution with high hydrophilicity has a viscosity average molecular weight of 10-40 ten thousand, a molecular weight distribution of 1-6, and a solid content of 18-25%.
9. The polyacrylonitrile spinning solution with high hydrophilicity prepared by the preparation method as claimed in claim 1.
10. The application of the polyacrylonitrile spinning solution with high hydrophilicity prepared by the preparation method of claim 1 in spinning.
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| CN1146209A (en) * | 1994-04-04 | 1997-03-26 | 施乐有限公司 | Aqueous polymerization processes |
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| CN105085797A (en) * | 2015-08-28 | 2015-11-25 | 国网智能电网研究院 | Polyacrylonitrile-based carbon fiber spinning solution and preparing method of polyacrylonitrile-based carbon fiber spinning solution |
| CN106279498A (en) * | 2016-08-16 | 2017-01-04 | 湖南兆恒材料科技有限公司 | A kind of high-performance PMI foam and preparation method thereof |
| CN106957435A (en) * | 2017-03-31 | 2017-07-18 | 中国工程物理研究院核物理与化学研究所 | It is a kind of to be used for polymer of uranium extraction and preparation method thereof in water body |
| WO2021065910A1 (en) * | 2019-09-30 | 2021-04-08 | 株式会社日本触媒 | Copolymer-containing detergent additive, soil release agent, microbial attachment inhibitor, fiber treatment agent, water treatment agent formulation, and coating formulation |
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2022
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146209A (en) * | 1994-04-04 | 1997-03-26 | 施乐有限公司 | Aqueous polymerization processes |
| CN102102234A (en) * | 2010-12-22 | 2011-06-22 | 中国科学院山西煤炭化学研究所 | Ternary copolymerization highly hydrophilic polyacrylonitrile-based carbon fiber spinning solution and preparation method thereof |
| CN105085797A (en) * | 2015-08-28 | 2015-11-25 | 国网智能电网研究院 | Polyacrylonitrile-based carbon fiber spinning solution and preparing method of polyacrylonitrile-based carbon fiber spinning solution |
| CN106279498A (en) * | 2016-08-16 | 2017-01-04 | 湖南兆恒材料科技有限公司 | A kind of high-performance PMI foam and preparation method thereof |
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