WO2004065434A1 - 炭素繊維プレカーサー用ポリマー - Google Patents
炭素繊維プレカーサー用ポリマー Download PDFInfo
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- WO2004065434A1 WO2004065434A1 PCT/JP2004/000391 JP2004000391W WO2004065434A1 WO 2004065434 A1 WO2004065434 A1 WO 2004065434A1 JP 2004000391 W JP2004000391 W JP 2004000391W WO 2004065434 A1 WO2004065434 A1 WO 2004065434A1
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- Prior art keywords
- carbon fiber
- polymer
- fiber precursor
- component
- acrylonitrile
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Classifications
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/42—Nitriles
- C08F20/44—Acrylonitrile
-
- 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
- C08F2/36—Polymerisation in solid state
-
- 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
-
- 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
Definitions
- the present invention relates to a polymer for a carbon fiber precursor capable of producing carbon fibers, a carbon fiber precursor obtained by spinning the polymer, and a flameproof carbon fiber precursor obtained by heat treating the polymer. More specifically, the present invention provides a method for controlling the stereoregularity of acrylonitrile repeating units constituting polyacrylonitrile, thereby lowering the temperature of the flame-proof treatment, and reducing the energy and time required for the flame-proof treatment.
- the present invention relates to a polymer for a carbon fiber precursor and a carbon fiber precursor capable of obtaining carbon fibers having high quality and high performance without causing fusion and thermal decomposition between fibers even when carbonization proceeds. Background art
- carbon fibers have excellent mechanical properties, especially high specific strength and specific elastic modulus, and are therefore widely used as reinforcing materials for various reinforcing materials such as aerospace, leisure goods and industrial materials. Its excellent mechanical properties are expected to reduce the weight of automobiles, and are attracting attention as part of the increasingly serious problem of reducing carbon dioxide.
- This carbon fiber is produced by subjecting a fiber prepared from an organic polymer, which is a precursor, to a flame-resistant treatment in the presence of oxygen, followed by firing and carbonization.
- the precursor include cellulose, phenolic resin, polypinyl alcohol, vinylidene chloride, pitch, and polyacrylonitrile (hereinafter sometimes abbreviated simply as PAN).
- PAN polyacrylonitrile
- a PAN-based precursor obtained by copolymerizing a specific amount of a polymerizable unsaturated carboxylic acid ammonium salt is used (see, for example, Patent Documents 1 and 2), or a long-chain alkylene of a polymerizable unsaturated carboxylic acid. It is disclosed that PAN obtained by copolymerizing an ester is used as a precursor (for example, see Patent Document 3).
- Patent Document 2 Japanese Patent Publication No. 58-48643
- Patent Document 4 Japanese Patent Publication No. 49-14404
- Patent Document 5 Japanese Patent Publication No. 6-27368
- Patent Document 6 Japanese Patent Application Laid-Open No. 11-117123
- Patent Document 9 JP-A-2-14013
- Non-Patent Document 1 W. Watt, et al., Proceding of the International Atlancheon Alcarb on fiberconference London , Paper No. 4, 1971 [Non-patent Document 2], A. Kob aso Va, et al., "VYS OKOMOLEKUL YARNYE SO ED I NEN I YA SER I YA A) ", Russia, 13 (1), 1971, p. 162-167
- Non-Patent Document 3 "MAS Geiderikh,” “VYS OKOMOLEKUL YARNYE S OED I NEN I YA SER I YA A ) J, Russia, 15 (6), 1973, P. 1239-1247.
- An object of the present invention is to solve the above-mentioned problems of the prior art, and to essentially reduce the temperature of the flame-proofing step without using a large amount of expensive and special monomers, thereby suppressing fusion and thermal decomposition between fibers. It is an object of the present invention to provide a polymer and a precursor for producing carbon fiber. BEST MODE FOR CARRYING OUT THE INVENTION
- the polymer for a carbon fiber precursor according to the present invention comprises a polymer having an acrylonitrile component in an amount of 50% by weight or more. Must be at least 35 mol% based on the total triad content of the constituent chains
- this polymer for a carbon fiber precursor it becomes possible to perform the oxidation treatment at a lower temperature and in a shorter time than in the case of carbon fiber production using a conventional atactic PAN-based polymer.
- the polymer for a carbon fiber precursor in the present invention means a so-called polymer before molding, such as a block or pellet, which is obtained by polymerizing a polymer containing 50% by weight or more of an acrylonitrile component and then performing arbitrary molding.
- the carbon fiber precursor according to the present invention is formed into a fibrous form through a spinning process such as wet spinning, dry-wet spinning, or dry spinning after polymerizing a polymer containing 50% by weight or more of an acrylonitrile component. It refers to the state in which it has been closed. That is, it shows up to the state before performing the flame resistance treatment and the heating carbonization treatment.
- the above-mentioned polymer for a carbon fiber precursor according to the present invention must be obtained from a polymer having an acrylonitrile component of 50% by weight or more. If the acrylonitrile component is less than 50% by weight, atactic When compared with the case where a PAN-based copolymer is used, a sufficient effect for improving the oxidization resistance is not exhibited, and it is difficult to solve the problem of the present invention.
- the carbon fiber precursor polymer may be a single polymer of isotactic PAN having a stereotacticity of 35 mol% or more of isotactic tride. It may be a mixture of two or more polymers containing 0% by weight or more, or a copolymer polymerized so that the isotactic PAN contains 50% by weight or more.
- the polymer for a carbon fiber precursor according to the present invention comprises a copolymer having an acrylonitrile component, an acrylic acid-based compound component and an acrylic ester-based compound component as main copolymerization components, wherein the acrylonitrile component is a copolymer. Preferably, it accounts for at least 80% by weight, and the sum of the weight percentages of the acrylic acid-based compound component and the acrylate ester-based compound component is more than 0% and less than 20%.
- main means that the total amount of the above three components (acrylonitrile component, acrylic acid-based compound component, and acrylate-based compound component) is preferably 80% by weight or more based on all copolymerized components. Means 90% by weight or more.
- the acrylonitrile component preferably accounts for 80% by weight or more based on the copolymer. At this time, a hexagonal mesh layer is sufficiently formed when the carbon fiber precursor is subjected to a flame-proofing step, The performance of the carbon fiber product will also be sufficient.
- the acrylonitrile component is preferably at least 90% by weight.
- the sum of the weight percentages of the acrylic acid-based compound component and the acrylic acid ester-based compound component is preferably more than 0% and less than 20%.
- the hexagonal mesh layer is sufficiently formed, and the performance of the carbon fiber product is also sufficient.
- the polymer of the present invention 1 3 C-NM R about a peak derived from Akuriro nitrile, estimated by, Akuriro ⁇ isotactic triad proportion of Akuri Ronitoriru constitutional sequence consisting of a nitrile component (mm preparative Raiado%) Is at least 35 mol% based on the total triad content of the acrylonitrile constituent chain composed of the acrylonitrile component. is necessary. If the carbon fiber precursor is not within the above range, the distance between adjacent members in the constituent chain is long, so that it is difficult to form a hexagonal mesh surface layer when the carbon fiber precursor is subjected to the flameproofing process, and the carbon obtained as the final product The mechanical strength of the fiber is not sufficient.
- the content ratio of the isotactic triad (mm triad%) is preferably at least 65 mol% based on the total triad content ratio of the acrylonitrile constituent chain composed of the acrylonitrile component.
- the isotactic triad content ratio (mm triad%) is defined as three consecutive repeating units (constituent chains are triads) in an addition-polymerized polymer. It means that the side chains of the monomer units are all in a meso (abbreviated as m) arrangement.
- triads include a heterotactic triad (m r) and a syndiotactic triad ( ⁇ r).
- m r indicates the relationship of the racemo arrangement.
- the isotactic triad content ratio is the ratio of mm in the mm, mr, and rr triads.
- this copolymer component may be a copolymerizable unsaturated compound.
- any of conventionally known compounds may be used, but unsaturated carboxylic acids and / or unsaturated carboxylic acid esters, particularly acrylic acid, methacrylic acid, itaconic acid and / or their alkyl esters It is preferable to use steal.
- alkyl ester examples include esters having an alkyl group having 1 to 6 carbon atoms, such as at least one group selected from methyl, ethyl, propyl, isopropyl, normal butyl, isobutyl, t-butyl group, and cyclohexyl. It can be preferably used.
- copolymerizable components include acrylonitrile component, acrylic compound, acrylate compound, methacrylnitrile, acetic acid pier, acrylamide, maleic anhydride, polar biel monomer such as N-vinylpyrrolidone, styrene, Aromatic pinyl compounds such as vinylpyridine and vinylimidazole can also be preferably used.
- copolymerization components may be used alone or in combination.
- acrylic acid, methacrylic acid, methacrylic acid, itaconic acid, or their alkyl esters, methacrylonitrile, vinyl acetate, acrylamide, maleic anhydride, and N-bipyrrolidone may be used.
- At least one compound selected from the group consisting of an aromatic vinyl compound such as a polar vinyl monomer such as styrene, vinyl pyridine, and pinyl imidazole can be preferably selected, and particularly, as described above, an acrylonitrile component and an acrylic acid It is preferable to use an acrylic compound or an acrylate compound.
- the role of other copolymer components is to suppress self-heating due to the intramolecular cyclization reaction in flame resistance and reduce thermal damage to the carbon fiber precursor. Excessive copolymerization may lead to a decrease in the performance of the carbon fiber.
- the combined component is less than 20 mol% in the carbon fiber precursor polymer.
- the method for producing the polymer for a carbon fiber precursor of the present invention is not particularly limited as long as it is a method capable of producing isotactic PAN, but effective methods are described in, for example, DM White et al., J, Am. Chem.
- ⁇ -type compound it is preferable to use a metal compound in a crystalline state belonging to Group I 1 VIII to Group IB of the periodic table.
- a halide it is preferable to use a halide.
- the metal compound in a crystalline state particularly has a structure in which metal cations and anions forming a pair with the metal cations are arranged in an orderly manner.
- the acrylonitrile component and the unsaturated copolymer component have a hydroxyl group, an amide group, or a carboxy group. It can coordinate to a metal cation via an unpaired electron on the oxygen or nitrogen atom contained in the acid ester group.
- the arrangement of the acrylonitrile component and the unsaturated copolymer component is regulated according to the order and size of the metal cation and the anion, or the distance between the ions.
- the halide of a metal belonging to the Periodic Table I Groups 18 to 1 IB is an isotactic stereocontrolled ⁇ -type compound. It is preferably used.
- Examples include iron chloride, cobalt chloride, nickel chloride, manganese chloride, chromium chloride, anhydrous magnesium chloride, anhydrous calcium chloride, anhydrous lanthanum chloride, anhydrous yttrium chloride, iron bromide, cobalt bromide, nickel bromide.
- the metal compound has a crystal system of a hexagonal system and / or a trigonal system.
- Many of these hexagonal and trigonal metal compounds have a layered structure when viewed macroscopically.
- the polar groups can be oriented in the same direction and arranged regularly.
- Such hexagonal and / or trigonal metal compound Calcium bromide hexahydrate, calcium iodide, calcium iodide hexahydrate, cobalt chloride (11), cobalt bromide (11), cobalt iodide (11), cobalt iodide (II) hexa Hydrate, cesium nitrate, cadmium chloride, cadmium bromide, cadmium iodide, iron chloride (1 1), iron chloride (III), iron bromide (1 1), iron bromide (III), iron Iron (II), potassium disulfide, potassium nitrite dihydrate, lithium iodide trihydrate, magnesium chloride, magnesium bromide hexahydrate, magnesium hydroxide, manganese chloride (11), odor Manganese (1 1), sodium nitrite, nickel (II) chloride, tin sulfate dihydrate, titanium chloride (1 1), titanium chloride (1 1 1), vanadium chloride
- magnesium chloride is particularly preferred.
- the acrylonitrile component and the unsaturated copolymer component may be brought into contact with a type III compound to form a complex. It is preferable to carry out the reaction under an inert gas atmosphere. If a mixed gas containing oxygen such as air is used, it may cause deactivation of radical growth terminals, and eventually a carbon fiber precursor having a sufficient degree of polymerization may be used. Boilers are difficult to obtain.
- the molar ratio (A / M) between one monomer component and a metal compound in a crystalline state belonging to Groups I1 to 1IB of the periodic table is 0.1 or more.
- the amount of the monomer component coordinated with the ⁇ -type compound is optimal for obtaining a high molecular weight compound, and is not affected by the excess monomer component. Therefore, the stereoregularity of the obtained copolymer for carbon fiber precursor can be further enhanced.
- the particle size of the metal compound in a crystalline state is also important, and a carbon fiber precursor capable of sufficiently spinning and having a viscosity average molecular weight (hereinafter sometimes simply referred to as Mv) of 50,000 or more.
- Mv viscosity average molecular weight
- the particle size of the metal compound is preferably 1 to less than 100 mm, more preferably 5 to less than 50 mm.
- Mv of the obtained carbon fiber precursor polymer becomes 50,000 or less, and spinning becomes extremely difficult. Conversely, if the particle size is 100 mm or more, the time required for the monomer component to infiltrate into the metal compound and complete the complex formation becomes long, and the degree of complex formation is not good. Not good for uniformity.
- the latter is desirably avoided because it causes Mv variation in the subsequent solid-state polymerization reaction.
- the complex prepared as described above is transferred to an appropriate container under an inert gas atmosphere, and then a solid-state polymerization reaction is performed.
- the solid-state polymerization reaction method can be roughly classified into two types, one is a thermal solid-state polymerization reaction in which a reaction initiator capable of generating radical species by thermal decomposition is present, and the other is a solid-state polymerization reaction.
- the reaction initiator in the present invention may be any one which is usually used as a reaction initiator in a radical polymerization reaction, and may be azobisisobutyl nitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2 , 2, -azobis (4-methoxy 2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate), 1,1- (cyclohexane-11-carbonitrile), Azo compounds represented by 2,2-azobis (2-methylbutyronitrile) and 2,2-azobis [N- (2-propenyl) -2-methylpropionamide], represented by benzoyl peroxide Organic peroxide, potassium peroxysulfate, sodium redisulfite, N, N-dimethylaniline-no-benzoyl peroxide, a redox initiator such as benzoyl peroxide, manganese acetyl acetate (111), cobalt acetyl acet
- the electromagnetic wave solid-state polymerization has an advantage that it is not necessary to particularly add a reaction initiator to generate radicals by irradiation with electromagnetic waves.
- the electromagnetic wave used here may be one having sufficient energy to generate radicals in the monomer molecule, such as ultraviolet light, X-ray, ⁇ -ray monochromatic visible light, natural light, electron beam, etc. Can be
- Temperature conditions suitable for the solid-state polymerization reaction are from 180 ° C to less than 150 ° C. If the temperature is lower than 80 ° C, not only the polymerization reaction rate will be extremely reduced, but also the problem of increased energy consumption for cooling will occur. Conversely, above 150 ° C, the monomer dissociates as a gas from the crystalline metal compound. It is not possible to obtain a polymer with sufficient Mv for the carbon fiber precursor.
- the complex that has undergone the solid-state polymerization reaction is composed of a crystalline metal compound and a monomer for the carbon fiber precursor. Accordingly, it is possible to finally obtain a polymer for a carbon fiber pressurizer as a residue eluted with water, methanol, ethanol or the like.
- composition of the obtained polymer and the activity of the polyacrylonitrile main chain can be quantitatively identified by 1 H-NMR and 13 C-NMR.
- the polymer for a carbon fiber precursor of the present invention obtained by the above-mentioned production method or the like can be produced by a conventionally known technique. Although there is no particular limitation on the specific spinning method, an ordinary wet spinning method, a dry spinning method, a dry-wet spinning method, or the like is used. In the present invention, the polymer yarn for the carbon fiber precursor obtained at this time is referred to as a carbon fiber precursor. In some cases, the flame resistance of the isotactic rich PAN unit partially progresses due to heat treatment such as drawing in the spinning process, and those containing these modified structures are also included in the carbon fiber precursor of the present invention. Included in the range.
- the carbon fiber precursor of the present invention can be obtained by subjecting a carbon fiber precursor to a heat and oxidation treatment at a temperature of 150 to 300 ° C. in an inert gas atmosphere at a temperature of 300 to 200 ° C. It is converted to carbon fiber through a graphite growth process of at least 0000 ° C and less than 2,500 ° C.
- An inert gas atmosphere such as nitrogen can be used as the atmosphere for the flameproofing treatment, but an active gas atmosphere such as air is more preferable because it shortens the flameproofing treatment time. .
- the carbon fiber At a low carbonization temperature of less than 300 ° C, the carbon fiber There is a problem that the elastic modulus of fiber decreases.
- the above carbon fibers can be further subjected to surface treatment, oil application, and sizing treatment as required.
- the flameproofing reaction involves an intramolecular cyclization reaction of adjacent nitrile groups in a constituent chain. It is considered that the reaction proceeds with a smaller activation energy. Therefore, it is considered that the oxidation treatment can be performed at a low temperature in the isotactic structure.
- the carbon fiber precursor has a 3/1 helical structure induced by isotacticity, a linear condensed pyridine ring, that is, a binaphthyridine skeleton is formed during the flame-proofing step.
- the monomer conversion rate in the polymerization and the composition of the obtained polymer were obtained from 1 H-NMR, and the stereoregularity (tacticity) of the polymer was measured by 13 C—NMR measurement (270 MHz JNR-EX). -270 Quantitative analysis using JEOL datum Co., Ltd., solvent DMSO-d6) The content ratio of the solid triad (mm%), the content ratio of the syndiotactic triad 7 (rr%), and the content ratio of the heterotactic triad (m ⁇ %) were determined.
- anhydrous magnesium chloride which is a hexagonal crystal having a particle size of a type I compound of 1 Omm or more and less than 30 mm, was placed in a three-necked flask, and kept at 10 ° C or less in an ice bath.
- this three-necked flask was set in a hot-air circulation dryer, and solid-state polymerization was performed at 70 ° C. for 12 hours. After solid-phase polymerization, the complex is poured into methanol, and anhydrous magnesium chloride is dissolved and extracted.Then, methanol-insoluble copolymer for carbon fiber precursor is collected by filtration, washed with ion-exchanged water and acetone in this order. .. Vacuum dried at 40 ° C. overnight.
- the obtained copolymer for carbon fiber precursor was 18.2 ⁇ (yield 65.4 %).
- the acrylonitrile component, methyl acrylate component, and dibutyl itaconate component were 94.5%, 2.4%, and 3.1%, respectively.
- anhydrous magnesium chloride having a hexagonal system and having a particle size of 10 mm or more and less than 30 mm as a ⁇ -type compound was placed in a three-necked flask, and kept at 10 ° C. or lower in an ice bath.
- a separately prepared three-necked flask was purged with nitrogen, and 34.6 ml of acrylonitrile, 2.0 ml of methyl acrylate, and 1.2 ml of dibutyl itaconate were mixed to obtain a monomer solution. This was added to anhydrous magnesium chloride and absorbed completely to prepare a complex of AZM2 1/1.
- the three-necked flask and the 300 ml screw-necked glass bottle were placed in a nitrogen-purged glove box, and the complex was transferred from the three-necked flask to the screw-necked glass bottle.
- the screw-cap glass bottle containing the complex was placed in an A-ray irradiation apparatus using a 6 QC0 radiation source, and electromagnetic wave solid-state polymerization was performed at a dose of 10 KGy.
- the obtained carbon fiber precursor copolymer was 16.6 g (yield 59.5%).
- Example 1 The same operation as in Example 1 was carried out except that anhydrous magnesium chloride was used instead of anhydrous magnesium chloride.
- the complex was poured into 5% by weight of dilute hydrochloric acid, and anhydrous chloride was extracted and removed, whereby a copolymer for a carbon fiber precursor insoluble in dilute hydrochloric acid was collected by filtration. Further, this was washed with ion-exchanged water and acetone in this order, and then dried under reduced pressure at 40 ° C. overnight.
- the obtained copolymer for carbon precursor was 11.9 g (yield 42.7%).
- the composition of the copolymer was estimated by 1 H-NMR measurement, the acrylonitrile component, methyl acrylate component, and dibutyl itaconate component were 93.3%, 2.8%, and 3.9%, respectively.
- 13 C-NMR measurement was performed to determine the tacticity.
- mmZmr / rr was 85.1 / 13.1 / 1.8, and it was confirmed that the sample had high isotacticity.
- Example 3 A similar operation was performed as in Example 3, except that anhydrous iron chloride having a hexagonal system was used instead of anhydrous cobalt chloride.
- the obtained copolymer for a carbon precursor was 14.4 g (yield 51.6 %) Met.
- the composition of the copolymer was estimated by 1 H-NMR measurement, the acrylonitrile component, methyl acrylate component, and dibutyl itaconate component were 95.7%, 2.6%, and 1.7%, respectively.
- Example 2 The same operation as in Example 1 was carried out except that 42 g of orthorhombic beryllium chloride was used instead of anhydrous magnesium chloride.
- the obtained carbon precursor copolymer was 17.1 g (yield 61.3
- the composition of the copolymer was estimated by .1H-NMR measurement, the acrylonitrile component, methyl acrylate component, and dibutyl itaconate component were 95.4%, 2.9%, and 1.7%, respectively.
- the procedure was the same except that 50 g of dimethyl alcohol, 103.8 ml of acrylonitrile, 6.0 ml of methyl acrylate, 3.6 ml of dibutyl itaconate, and 75 g of azobisisobutyronitrile were mixed. .
- the obtained copolymer for a carbon precursor was 82.2 g (yield 91.8.%).
- the composition of the copolymer was estimated by 1 H—NMR measurement, the acrylonitrile component, methyl acrylate component, and dibutyl itaconate component were 95.9%, 2.5%, and 1.6%, respectively. Met.
- Example 2 The same operation was performed as in Example 1, except that fine powdered magnesium chloride having a particle size of 1 xm or less was used.
- the composition of the copolymer was estimated by 1 H—NMR measurement, the acrylonitrile component, methyl acrylate component, and dibutyl itaconate component were 95.5%, 2.7%, and 1.8%, respectively. %Met.
- Example 1 A similar construction was performed in Example 1 except that only acrylonitrile was used as a raw material without using methyl acrylate or dibutyl itaconate.
- the amount of the obtained carbon precursor polymer was 18.8 g (yield: 67.7%).
- the obtained amount of the copolymer for a carbon precursor was 21.9 g (yield 78.5%).
- the acrylonitrile component, the methyl acrylate component, and the dibutyl itaconate component were 95.3% and 2.9%, respectively. %Met.
- the mm / mrZr r was 27.0 / 50.4 / 22.6, indicating that a real atactic copolymer for a carbon fiber precursor was obtained.
- the intrinsic viscosity obtained using a Ube-Ide type viscometer in N, N, -dimethylformamide at 35 ° C was 1.83.
- the exothermic peak copolymerization temperature of the carbon fiber precursor-rich copolymer of the working example was higher than that of the comparative example having a larger atactic structure, because the exothermic peak top temperature due to the cyclization reaction during the oxidation treatment was shifted to a lower temperature side.
- the carbon fiber precursor is effective as a polymer for a carbon fiber precursor and a carbon fiber precursor, which is excellent in oxidization resistance.
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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JP2005508076A JP4137940B2 (ja) | 2003-01-23 | 2004-01-20 | 炭素繊維プレカーサー用ポリマーの製造方法 |
US10/542,805 US7338997B2 (en) | 2003-01-23 | 2004-01-20 | Polymer for carbon fiber precursor |
DE602004019759T DE602004019759D1 (de) | 2003-01-23 | 2004-01-20 | Festphasenpolymerimerisation |
KR1020057013430A KR101047819B1 (ko) | 2003-01-23 | 2004-01-20 | 탄소 섬유 전구체용 중합체 |
EP04703472A EP1589042B1 (en) | 2003-01-23 | 2004-01-20 | Solid phase polymerisation |
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JP2003-426454 | 2003-12-24 |
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EP (1) | EP1589042B1 (ja) |
JP (1) | JP4137940B2 (ja) |
KR (1) | KR101047819B1 (ja) |
AT (1) | ATE424425T1 (ja) |
DE (1) | DE602004019759D1 (ja) |
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US20190293139A1 (en) | 2018-03-26 | 2019-09-26 | Goodrich Corporation | Carbon fiber crystal orientation improvement by polymer modification, fiber stretching and oxidation for brake application |
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WO2020252031A1 (en) * | 2019-06-11 | 2020-12-17 | University Of Virginia Patent Foundation | System and method of accelerating polymer fiber stabilization via irradiation treatment |
CN114621391B (zh) * | 2022-04-01 | 2023-06-20 | 安徽大学 | 碳纤维原丝用聚丙烯腈的电子束转靶x射线辐射聚合方法 |
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- 2004-01-20 AT AT04703472T patent/ATE424425T1/de not_active IP Right Cessation
- 2004-01-20 US US10/542,805 patent/US7338997B2/en not_active Expired - Fee Related
- 2004-01-20 WO PCT/JP2004/000391 patent/WO2004065434A1/ja active Application Filing
- 2004-01-20 KR KR1020057013430A patent/KR101047819B1/ko not_active IP Right Cessation
- 2004-01-20 TW TW093101654A patent/TW200418888A/zh not_active IP Right Cessation
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JP2006016482A (ja) * | 2004-07-01 | 2006-01-19 | Teijin Ltd | 立体規則性を有する炭素繊維プレカーサ用共重合体の製造方法 |
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JP2014012918A (ja) * | 2009-03-31 | 2014-01-23 | Donghua Univ | 炭素繊維及びその原糸、プレ酸化繊維の製造方法 |
JP2011006294A (ja) * | 2009-06-26 | 2011-01-13 | Teijin Ltd | 炭素材料及びその製造方法 |
JP2011195362A (ja) * | 2010-03-18 | 2011-10-06 | Teijin Ltd | 炭素材料及びその製造方法 |
JP2011213586A (ja) * | 2010-03-18 | 2011-10-27 | Teijin Ltd | 炭素材料及びその製造方法 |
CN102382623A (zh) * | 2011-08-02 | 2012-03-21 | 山东大学 | 一种碳基复合吸波材料的制备方法 |
JP2014087794A (ja) * | 2013-11-26 | 2014-05-15 | Seizo Miyata | 炭素触媒の製造方法 |
WO2023008273A1 (ja) * | 2021-07-26 | 2023-02-02 | 東レ株式会社 | 炭素繊維束およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
TW200418888A (en) | 2004-10-01 |
TWI297693B (ja) | 2008-06-11 |
US20060183834A1 (en) | 2006-08-17 |
DE602004019759D1 (de) | 2009-04-16 |
KR20050100635A (ko) | 2005-10-19 |
EP1589042A1 (en) | 2005-10-26 |
ATE424425T1 (de) | 2009-03-15 |
US7338997B2 (en) | 2008-03-04 |
EP1589042B1 (en) | 2009-03-04 |
JPWO2004065434A1 (ja) | 2006-05-18 |
KR101047819B1 (ko) | 2011-07-08 |
EP1589042A4 (en) | 2006-11-22 |
JP4137940B2 (ja) | 2008-08-20 |
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