CN114621391B - Electron beam target-rotating X-ray radiation polymerization method of polyacrylonitrile for carbon fiber precursor - Google Patents
Electron beam target-rotating X-ray radiation polymerization method of polyacrylonitrile for carbon fiber precursor Download PDFInfo
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- CN114621391B CN114621391B CN202210338864.9A CN202210338864A CN114621391B CN 114621391 B CN114621391 B CN 114621391B CN 202210338864 A CN202210338864 A CN 202210338864A CN 114621391 B CN114621391 B CN 114621391B
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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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/54—Polymerisation initiated by wave energy or particle radiation by X-rays or electrons
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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
The invention discloses an electron beam-to-target X-ray radiation polymerization method of polyacrylonitrile for carbon fiber precursors, which relates to the technical field of polyacrylonitrile preparation, and adopts acrylonitrile and vinyl comonomers as raw materials, and uses X rays generated by electron beam bombardment of an X-ray conversion target to carry out radiation polymerization, so that no additional heat source or chemical initiator is needed, the influence of PAN fiber performance reduction caused by initiator residues is avoided, and energy-saving, environment-friendly, low-carbon emission and green production can be realized; the method has the advantages that the energy of the X-ray is high, the direction is concentrated, the radiation source cannot be attenuated, the use efficiency is high, the method is safe and controllable, the polymerization reaction time can be greatly shortened, the reaction process is stable, and the product performance is high; the PAN polymer prepared by the method has high molecular weight, narrow molecular weight distribution, stable thermal performance and regular molecular chain structure, can be used for preparing ultra-high strength PAN-based carbon fibers, and is widely applied to the fields of national defense and military industry, aerospace and aviation, sports equipment, industrial parts and the like.
Description
Technical field:
the invention relates to the technical field of Polyacrylonitrile (PAN) preparation, in particular to an electron beam targeting X-ray radiation polymerization method of polyacrylonitrile for carbon fiber precursors.
The background technology is as follows:
the super PAN-based carbon fiber can be widely applied to the fields of national defense and military industry, aerospace, sports equipment, earthquake-resistant building materials, industrial parts, storage tanks, high-energy density fuel cells and the like due to the characteristics of light specific gravity, high strength, high modulus, high temperature resistance, good fatigue resistance and the like. In the preparation process of PAN-based carbon fiber, the performance of the PAN for spinning plays a crucial role in the final performance of the super-strong carbon fiber. And the ultra-high molecular weight PAN fiber can prepare the ultra-high strength carbon fiber.
The PAN polymer is prepared by adopting a chemical initiator to carry out thermal initiation polymerization at home and abroad, but the PAN polymer prepared by the method has low molecular weight, wide molecular weight distribution and low yield, cannot meet market demands, and the chemical initiator can remain in the PAN polymer to influence the thermal performance of the PAN polymer, so that the performance of PAN fibers is influenced, and the production of the ultra-high strength carbon fibers is not facilitated.
The invention comprises the following steps:
the technical problem to be solved by the invention is to provide an electron beam target-rotating X-ray radiation polymerization method of polyacrylonitrile for carbon fiber precursor, which is not reported at home and abroad at present. The invention uses acrylonitrile and alkene comonomer as raw materials, uses X-ray to irradiate and initiate polymerization reaction of high polymer material, avoids the influence of PAN polymer performance reduction caused by chemical initiator residue, and the prepared PAN polymer has regular structure, high molecular weight and narrow molecular weight distribution, the ultrahigh molecular weight can improve the high strength of PAN-based fiber, and the narrower molecular weight distribution can lead the strength distribution of each part of the fiber to be uniform, reduce the yarn breakage phenomenon generated in continuous fiber production and improve the spinning productivity.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
an electron beam targeting X-ray radiation polymerization method of polyacrylonitrile for carbon fiber precursors comprises the following steps:
(1) Sequentially adding acrylonitrile, vinyl comonomer and deionized water into a tubular reactor according to a proportion, mixing, introducing inert gas to deoxidize, bombarding X-rays generated by an X-ray conversion target by using electron beams, and irradiating for a certain time at a certain temperature to perform polymerization reaction to obtain PAN suspension;
(2) And centrifuging the PAN suspension by using a high-speed separation device, washing, filtering and vacuum drying to obtain PAN powder.
The inert gas is nitrogen or argon.
The weight parts of the acrylonitrile and the vinyl comonomer are 100 parts of the acrylonitrile and 1.0 to 6.0 parts of the vinyl comonomer. Preferably, the vinyl comonomer is 1.5 to 4.0 parts.
In the step (1), the mass concentration of acrylonitrile and vinyl comonomer is regulated to be 2.0-8.0%, preferably 5.0-7.0% by using deionized water.
The vinyl comonomer is one or a mixture of more than one of itaconic acid, methyl itaconate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, acrylamide, styrene, vinyl chloride and vinylidene chloride in any proportion.
The tubular reactor is one or more of a horizontal tubular reactor, a U-shaped tubular reactor, a vertical pipe reactor, a coil pipe reactor and a multi-pipe parallel tubular reactor.
The polymerization reaction temperature is 10-60 ℃, and the irradiation reaction time is 10-120 s.
The polymerization reaction is completed when the radiation irradiation is carried out under the dosage rate of 2000Gy/s and the absorbed dosage is 20-120 kGy.
The high-speed separation device is a tubular high-speed separator or an ultra-high-speed refrigerated centrifuge. The rotation speed of the centrifugal machine is 5000-18000 rpm, and the mesh number of the screen is 1000-12000.
The vacuum drying temperature is 60-80 ℃.
The beneficial effects of the invention are as follows:
(1) In the preparation process of the method, the X-rays generated by the electron beam conversion target are used for PAN radiation polymerization, and no additional heat source or chemical initiator is needed, so that the influence of the reduction of PAN fiber performance caused by initiator residues is avoided, and the energy-saving, environment-friendly, low-carbon emission and green production can be realized.
(2) The method uses the electron beam to bombard the X-ray generated by the X-ray conversion target for irradiation, and has the advantages of high X-ray energy, concentrated direction, no attenuation of the ray source, high use efficiency, safety and controllability, greatly shortened polymerization reaction time, stable reaction process and high product performance.
(3) The PAN polymer prepared by the method has high molecular weight, narrow molecular weight distribution, stable thermal performance and regular molecular chain structure, can be used for preparing ultra-high strength PAN-based carbon fibers, and is widely applied to the fields of national defense and military industry, aerospace and aviation, sports equipment, industrial parts and the like.
Drawings
Fig. 1 is a block diagram of a preparation flow of PAN polymer.
The specific embodiment is as follows:
the invention is further described in connection with the following embodiments in order to make the technical means, the creation features, the achievement of the purpose and the effect of the invention easy to understand.
Example 1
(1) 6 parts of acrylonitrile, methyl acrylate, itaconic acid and 94 parts of deionized water with the proportion of 100:2.5:1 are sequentially added into a horizontal tubular reactor according to the proportion to be mixed, and inert gas N is introduced 2 Deoxidizing for 20min, irradiating X-ray generated on the X-ray conversion target material by using an electron beam, and irradiating for 20s at 40 ℃ to perform polymerization reaction to prepare PAN suspension.
(2) And centrifuging the PAN suspension for 5min at 8000r/min by using a tubular high-speed separator, washing with deionized water for several times, filtering with a 3000-mesh screen, and drying at 55 ℃ by using a vacuum oven to obtain PAN powder.
Example 2
(1) Sequentially adding 5 parts of acrylonitrile, methyl acrylate, itaconic acid and 95 parts of deionized water in a ratio of 100:1.5:1.5 into a horizontal tubular reactor according to a proportion, mixing, and introducing inert gas N 2 Deoxidizing for 20min, irradiating X-ray generated on the X-ray conversion target material by using an electron beam, and irradiating for 40s at 35 ℃ to perform polymerization reaction to prepare PAN suspension.
(2) And centrifuging the PAN suspension for 5min at 10000r/min by using a tubular high-speed separator, washing with deionized water for several times, filtering with a 5000-mesh screen, and drying at 55 ℃ by using a vacuum oven to obtain PAN powder.
Example 3
(1) The proportion of 7 parts is 100:2.5:1.5 acrylonitrile, methyl acrylate, itaconic acid and 93 parts deionized water are added into a horizontal tubular reactor in sequence according to the proportion for mixing, and inert gas N is introduced 2 Deoxidizing for 20min, irradiating X-ray generated on the X-ray conversion target material by using an electron beam, and irradiating for 60s at 50 ℃ for polymerization reaction to prepare PAN suspension.
(2) And centrifuging the PAN suspension for 5min at 11000r/min by using a tubular high-speed separator, washing with deionized water for several times, filtering with a 3000-mesh screen, and drying at 55 ℃ by using a vacuum oven to obtain PAN powder.
Example 4
(1) 6 parts of acrylonitrile, methyl acrylate, itaconic acid and 94 parts of deionized water with the proportion of 100:2:1.5 are sequentially added into a horizontal tubular reactor according to the proportion for mixing, inert gas argon is introduced for deoxidizing for 20min, X-rays generated on an X-ray conversion target material are irradiated by an electron beam, and polymerization reaction is carried out by irradiation for 40s at 60 ℃ to prepare PAN suspension.
(2) And centrifuging the PAN suspension for 5min at a speed of 12000r/min by using a tubular high-speed separator, washing with deionized water for several times, filtering with a 5000-mesh screen, and drying at 55 ℃ by using a vacuum oven to obtain PAN powder.
Comparative example 1 (polymerization Using chemical initiator)
(1) At N 2 Under the protection of (2), 6 parts of acrylonitrile, methyl acrylate, itaconic acid and 94 parts of deionized water with the proportion of 100:1.5:1.5 are sequentially added into a three-necked flask according to the proportion, stirred, and dropwise added with an initiator azodiisobutyronitrile (accounting for 1.5% of the total monomer mass) to react for 3 hours at 60 ℃ for free radical polymerization reaction, so as to prepare PAN suspension.
(2) And centrifuging the PAN suspension for 5min at 8000r/min by using a tubular high-speed separator, washing with deionized water for several times, filtering with a 5000-mesh screen, and drying at 55 ℃ by using a vacuum oven to obtain PAN powder.
Comparative example 2 (polymerization with Co 60 radiation)
(1) 6 parts of acrylonitrile, methyl acrylate, itaconic acid and 94 parts of deionized water with the proportion of 100:1.5:1.5 are placed in a radiation bottle for stirring, and inert gas N is introduced 2 Deoxidizing for 20min, placing the radiation bottle in cobalt 60 sourceAfter 3h of irradiation at 60℃in the chamber, a PAN suspension was prepared.
(2) And centrifuging the PAN suspension for 5min at 8000r/min by using a tubular high-speed separator, washing with deionized water for several times, filtering with a 5000-mesh screen, and drying at 55 ℃ by using a vacuum oven to obtain PAN powder.
TABLE 1 Performance test results data for the PAN polymers obtained in examples 1-4 and comparative examples 1-2 described above
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. An electron beam-targeting X-ray radiation polymerization method of polyacrylonitrile for carbon fiber precursors is characterized by comprising the following steps:
(1) Sequentially adding acrylonitrile, vinyl comonomer and deionized water into a tubular reactor according to a proportion, mixing, introducing inert gas to deoxidize, bombarding X-rays generated by an X-ray conversion target by using electron beams, and irradiating for a certain time at a certain temperature to perform polymerization reaction to obtain PAN suspension;
(2) Centrifuging, washing, filtering and vacuum drying the PAN suspension by using a high-speed separation device to obtain PAN powder;
the polymerization reaction temperature is 10-60 ℃, and the irradiation reaction time is 10-120 s;
the weight parts of the acrylonitrile and the vinyl comonomer are 100 parts of acrylonitrile and 1.0-6.0 parts of vinyl comonomer;
in the step (1), deionized water is used for adjusting the mass concentration of acrylonitrile and vinyl comonomer to 2.0-8.0%;
the polymerization reaction is completed when the radiation is carried out at the dose rate of 2000Gy/s until the absorbed dose is 20-120 kGy.
2. The electron beam-mediated X-ray radiation polymerization process according to claim 1, wherein: the inert gas is nitrogen or argon.
3. The electron beam-mediated X-ray radiation polymerization process according to claim 1, wherein: the vinyl comonomer is one or a mixture of more than one of itaconic acid, methyl itaconate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, acrylamide, styrene, vinyl chloride and vinylidene chloride in any proportion.
4. The electron beam-mediated X-ray radiation polymerization process according to claim 1, wherein: the tubular reactor is one or more of a horizontal tubular reactor, a U-shaped tubular reactor, a vertical pipe reactor, a coil pipe reactor and a multi-pipe parallel tubular reactor.
5. The electron beam-mediated X-ray radiation polymerization process according to claim 1, wherein: the high-speed separation device is a tubular high-speed separator or an ultra-high-speed refrigerated centrifuge; the rotation speed of the centrifugal machine is 5000-18000 revolutions per minute, and the mesh number of the screen is 1000-12000 meshes.
6. The electron beam-mediated X-ray radiation polymerization process according to claim 1, wherein: the vacuum drying temperature is 60-80 ℃.
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