JP2019203107A - Carbon material precursor, carbon material precursor composition containing the same, and method for producing carbon material using the same - Google Patents
Carbon material precursor, carbon material precursor composition containing the same, and method for producing carbon material using the same Download PDFInfo
- Publication number
- JP2019203107A JP2019203107A JP2018100887A JP2018100887A JP2019203107A JP 2019203107 A JP2019203107 A JP 2019203107A JP 2018100887 A JP2018100887 A JP 2018100887A JP 2018100887 A JP2018100887 A JP 2018100887A JP 2019203107 A JP2019203107 A JP 2019203107A
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- Prior art keywords
- carbon material
- material precursor
- molecular weight
- yield
- acrylamide
- Prior art date
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 257
- 239000002243 precursor Substances 0.000 title claims abstract description 196
- 239000000203 mixture Substances 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 73
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims description 59
- 239000000654 additive Substances 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 abstract description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 89
- 229920001577 copolymer Polymers 0.000 description 44
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 39
- 230000015572 biosynthetic process Effects 0.000 description 30
- 239000003125 aqueous solvent Substances 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 24
- 239000012046 mixed solvent Substances 0.000 description 23
- 239000007864 aqueous solution Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 20
- 238000000465 moulding Methods 0.000 description 20
- 239000000178 monomer Substances 0.000 description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 11
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 11
- 235000019838 diammonium phosphate Nutrition 0.000 description 11
- -1 etc. Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229920002239 polyacrylonitrile Polymers 0.000 description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 7
- 238000009987 spinning Methods 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 238000001891 gel spinning Methods 0.000 description 5
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- 238000003756 stirring Methods 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
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- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
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- 238000002166 wet spinning Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001523 electrospinning Methods 0.000 description 3
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- 239000011261 inert gas Substances 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
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- 238000001291 vacuum drying Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
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- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- IJSVVICYGLOZHA-UHFFFAOYSA-N 2-methyl-n-phenylprop-2-enamide Chemical compound CC(=C)C(=O)NC1=CC=CC=C1 IJSVVICYGLOZHA-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
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- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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Abstract
Description
本発明は、炭素材料前駆体、それを含有する炭素材料前駆体組成物、及びそれらを用いた炭素材料の製造方法に関する。 The present invention relates to a carbon material precursor, a carbon material precursor composition containing the same, and a method for producing a carbon material using them.
炭素材料の１種である炭素繊維の製造方法としては、従来から、ポリアクリロニトリルを紡糸して得られる炭素繊維前駆体に耐炎化処理を施した後、炭化処理を施す方法が主として採用されている（例えば、特公昭３７−４４０５号公報（特許文献１）、特開２０１５−７４８４４号公報（特許文献２）、特開２０１６−４０４１９号公報（特許文献３）、特開２０１６−１１３７２６号公報（特許文献４））。この方法に用いられるポリアクリロニトリルは安価な汎用溶媒に溶解しにくいため、重合や紡糸の際に、ジメチルスルホキシドやＮ，Ｎ−ジメチルアセトアミド等の高価な溶媒を使用する必要があり、炭素繊維の製造コストが高くなるという問題があった。また、ポリアクリロニトリルに加熱処理を施すと、急激な発熱が起こり、ポリアクリロニトリルの熱分解が加速されるため、炭素材料（炭素繊維）の収率が低くなるという問題があった。このため、ポリアクリロニトリルを用いて炭素材料（炭素繊維）を製造する場合には、耐炎化処理や炭化処理の昇温過程において、急激な発熱が発生しないように、長時間をかけて徐々に昇温する必要があった。 As a method for producing carbon fiber, which is a kind of carbon material, conventionally, a method of subjecting a carbon fiber precursor obtained by spinning polyacrylonitrile to flame resistance treatment and then carbonization treatment has been mainly employed. (For example, Japanese Patent Publication No. 37-4405 (Patent Document 1), Japanese Patent Application Laid-Open No. 2015-74844 (Patent Document 2), Japanese Patent Application Laid-Open No. 2006-40419 (Patent Document 3), Japanese Patent Application Laid-Open No. 2006-113726 ( Patent Document 4)). Since polyacrylonitrile used in this method is difficult to dissolve in an inexpensive general-purpose solvent, it is necessary to use an expensive solvent such as dimethyl sulfoxide or N, N-dimethylacetamide during polymerization or spinning, which produces carbon fiber. There was a problem of high costs. In addition, when heat treatment is performed on polyacrylonitrile, rapid heat generation occurs and thermal decomposition of polyacrylonitrile is accelerated, resulting in a problem that the yield of carbon material (carbon fiber) is lowered. For this reason, when producing a carbon material (carbon fiber) using polyacrylonitrile, it gradually rises over a long period of time so that rapid heat generation does not occur during the temperature rise process of the flameproofing treatment or carbonization treatment. It was necessary to warm.
一方、ポリアクリルアミドは水溶性のポリマーであり、重合や成形加工（フィルム化、シート化、紡糸等）の際に、安価で環境負荷の小さい水を溶媒として使用することができるため、炭素材料の製造コストの削減が期待される。 Polyacrylamide, on the other hand, is a water-soluble polymer, and can be used as a solvent for water and low environmental impact during polymerization and molding (filming, sheeting, spinning, etc.). Reduction of manufacturing cost is expected.
しかしながら、従来の一般的なポリアクリルアミドを用いて作製した炭素材料前駆体は、耐炎化処理や炭化処理により質量が大きく減少し、得られる炭素材料の収率が低くなるという問題があることを本発明者らは見出した。 However, the carbon material precursor produced using conventional polyacrylamide has a problem that the mass is greatly reduced by the flameproofing treatment and carbonization treatment, and the yield of the obtained carbon material is low. The inventors have found.
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、アクリルアミド系ポリマーからなり、高収率で炭素材料を得ることが可能な炭素材料前駆体、それを含有する炭素材料前駆体組成物、及びそれらを用いた炭素材料の製造方法を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and is made of an acrylamide polymer, and a carbon material precursor capable of obtaining a carbon material in a high yield, and a carbon material precursor containing the carbon material precursor It aims at providing the manufacturing method of a composition and carbon material using them.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、アクリルアミド系ポリマーからなる炭素材料前駆体において、低分子量成分の含有率の小さいアクリルアミド系ポリマーを用いることによって、炭素材料の収率が向上することを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the inventors of the present invention have made it possible to obtain a carbon material precursor by using an acrylamide polymer having a low content of low molecular weight components in a carbon material precursor composed of an acrylamide polymer. The inventors have found that the rate is improved and have completed the present invention.
すなわち、本発明の炭素材料前駆体は、重量平均分子量が２万〜２００万であり、かつ、積分分子量分布曲線においてポリマー全体に対して分子量が５０００以下の低分子量成分の占める割合が７％以下であるアクリルアミド系ポリマーからなることを特徴とするものである。また、本発明の炭素材料前駆体組成物は、前記本発明の炭素材料前駆体と、酸及びその塩からなる群から選択される少なくとも１種の添加成分とを含有することを特徴とするものである。さらに、本発明の炭素材料の製造方法は、前記本発明の炭素材料前駆体又は前記本発明の炭素材料前駆体組成物に炭化処理を施すことを特徴とするものである。このような本発明の炭素材料の製造方法においては、前記炭化処理の前に、前記炭素材料前駆体又は前記炭素材料前駆体組成物に耐炎化処理を施すことが好ましい。 That is, the carbon material precursor of the present invention has a weight average molecular weight of 20,000 to 2,000,000, and the proportion of the low molecular weight component having a molecular weight of 5000 or less relative to the whole polymer in the integral molecular weight distribution curve is 7% or less. It is characterized by comprising an acrylamide polymer. The carbon material precursor composition of the present invention contains the carbon material precursor of the present invention and at least one additive component selected from the group consisting of acids and salts thereof. It is. Furthermore, the carbon material manufacturing method of the present invention is characterized in that carbonization treatment is performed on the carbon material precursor of the present invention or the carbon material precursor composition of the present invention. In such a method for producing a carbon material of the present invention, it is preferable to subject the carbon material precursor or the carbon material precursor composition to a flame resistance treatment before the carbonization treatment.
なお、本発明の炭素材料前駆体を用いることによって、炭素材料の収率が向上する理由は必ずしも定かではないが、本発明者らは以下のように推察する。すなわち、本発明の炭素材料前駆体は、低分子量成分の含有率が小さいアクリルアミド系ポリマーからなるものであるため、酸化性ガス存在下で加熱処理（耐炎化処理）を施しても、熱分解されにくく、多くの耐炎化物が生成する（炭素材料前駆体の耐炎化収率が高くなる）と推察される。また、耐炎化処理を施すと、アクリルアミド系ポリマーの分子内には、脱アンモニア反応や脱水反応によって耐熱性の高いイミド環構造が形成されたり、部分酸化反応等の後の脱水反応等によって不飽和結合が形成されたりするため、生成した耐炎化物も耐炎化処理において熱分解されにくくなり、炭素材料前駆体の耐炎化収率が更に高くなると推察される。さらに、生成した耐炎化物は、耐熱性に優れているため、不活性ガス雰囲気下での加熱処理（炭化処理）を施しても、熱分解されにくく、多くの炭素材料が生成する（耐炎化物の炭化収率が高くなる）と推察される。また、本発明の炭素材料前駆体組成物においては、比較的低温で耐炎化処理を施しても、添加成分である酸やその塩がアクリルアミド系ポリマーの脱アンモニア反応や脱水反応を大きく促進するため、アクリルアミド系ポリマー分子内には耐熱性の高いイミド環構造や不飽和結合が形成されやすく、生成した耐炎化物は耐炎化処理において更に熱分解されにくくなり、炭素材料前駆体の耐炎化収率が更に高くなると推察される。また、生成した耐炎化物は、耐熱性に更に優れているため、炭化処理を施しても、更に熱分解されにくく、更に多くの炭素材料が生成する（耐炎化物の炭化収率が更に高くなる）と推察される。 The reason why the yield of the carbon material is improved by using the carbon material precursor of the present invention is not necessarily clear, but the present inventors speculate as follows. That is, since the carbon material precursor of the present invention is made of an acrylamide polymer having a low content of low molecular weight components, it is thermally decomposed even when subjected to heat treatment (flame resistance treatment) in the presence of an oxidizing gas. It is difficult to produce a large number of flameproofed products (the flameproofing yield of the carbon material precursor is increased). In addition, when flame-resistant treatment is applied, acrylamide ring structure with high heat resistance is formed in the molecule of acrylamide polymer by deammonia reaction or dehydration reaction, or it is unsaturated by dehydration reaction after partial oxidation reaction, etc. Since bonds are formed, it is assumed that the produced flame-resistant product is not easily thermally decomposed in the flame-proofing treatment, and the flame-proofing yield of the carbon material precursor is further increased. Furthermore, since the produced flame-resistant product is excellent in heat resistance, even if it is subjected to a heat treatment (carbonization treatment) in an inert gas atmosphere, it is difficult to be thermally decomposed and many carbon materials are produced (of the flame-resistant product). It is inferred that the carbonization yield increases. In addition, in the carbon material precursor composition of the present invention, even if the flameproofing treatment is performed at a relatively low temperature, the additive component acid or salt thereof greatly accelerates the deammonification reaction or dehydration reaction of the acrylamide polymer. , Imide ring structures and unsaturated bonds with high heat resistance are easily formed in the acrylamide polymer molecule, and the resulting flame-resistant product is more difficult to be thermally decomposed in the flame-resistant treatment, resulting in a flame-resistant yield of the carbon material precursor. It is estimated that it will be even higher. In addition, since the flame-resistant product thus produced is further excellent in heat resistance, even if it is subjected to carbonization treatment, it is more difficult to be thermally decomposed and more carbon materials are produced (the carbonization yield of the flame-resistant product is further increased). It is guessed.
一方、低分子量成分の含有率が大きい一般的なアクリルアミド系ポリマーからなる炭素材料前駆体は、耐炎化処理によって熱分解されやすいため、耐炎化物の生成量が少なくなる（炭素材料前駆体の耐炎化収率が低くなる）と推察される。また、耐炎化処理を施しても、アクリルアミド系ポリマーの分子内に耐熱性の高いイミド環構造や不飽和結合が形成されにくいため、生成した耐炎化物も耐炎化処理によって熱分解されやすく、炭素材料前駆体の耐炎化収率が更に低くなると推察される。さらに、生成した耐炎化物は、耐熱性に劣るため、炭化処理によって熱分解されやすく、炭素材料の生成量が少なくなる（耐炎化物の炭化収率が低くなる）と推察される。 On the other hand, a carbon material precursor made of a general acrylamide polymer with a high content of low molecular weight components tends to be thermally decomposed by the flameproofing treatment, so that the amount of flameproofed product is reduced (the carbon material precursor is made flameproof). It is assumed that the yield is low). In addition, even if flameproofing treatment is applied, it is difficult to form an imide ring structure or unsaturated bond with high heat resistance in the molecule of the acrylamide polymer. It is presumed that the flameproofing yield of the precursor is further lowered. Furthermore, since the flame-resistant product produced is inferior in heat resistance, it is presumed that it is easily pyrolyzed by carbonization treatment, and the amount of carbon material produced is reduced (the carbonization yield of the flame-resistant product is reduced).
本発明によれば、アクリルアミド系ポリマーからなり、高収率で炭素材料を得ることが可能な炭素材料前駆体及びそれを含有する炭素材料前駆体組成物を得ることができる。また、このような炭素材料前駆体を用いることによって、効率よく炭素材料を製造することが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, the carbon material precursor which consists of an acrylamide type polymer and can obtain a carbon material with a high yield, and the carbon material precursor composition containing it can be obtained. Moreover, it becomes possible to manufacture a carbon material efficiently by using such a carbon material precursor.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
〔炭素材料前駆体〕
先ず、本発明の炭素材料前駆体について説明する。本発明の炭素材料前駆体は、重量平均分子量が２万〜２００万であり、かつ、積分分子量分布曲線においてポリマー全体に対して分子量が５０００以下の低分子量成分の占める割合が７％以下であるアクリルアミド系ポリマーからなるものである。
[Carbon material precursor]
First, the carbon material precursor of the present invention will be described. The carbon material precursor of the present invention has a weight average molecular weight of 20,000 to 2,000,000, and the proportion of the low molecular weight component having a molecular weight of 5000 or less relative to the whole polymer in the integral molecular weight distribution curve is 7% or less. It consists of an acrylamide polymer.
（アクリルアミド系ポリマー）
本発明に用いられるアクリルアミド系ポリマーの重量平均分子量は２万〜２００万である。アクリルアミド系ポリマーの重量平均分子量が前記上限を超えると、フィルム化、シート化、紡糸等における成形加工性（紡糸性）が低下する。他方、アクリルアミド系ポリマーの重量平均分子量が前記下限未満になると、アクリルアミド系ポリマーからなる炭素材料前駆体の強度が低下する。さらに、前記アクリルアミド系ポリマーの重量平均分子量の上限としては、成形加工性（紡糸性）が更に向上するという観点から、１５０万以下が好ましく、１００万以下がより好ましく、８０万以下が更に好ましく、５０万以下がまた更に好ましく、３０万以下が特に好ましく、２０万以下が最も好ましい。また、アクリルアミド系ポリマーの重量平均分子量の下限としては、アクリルアミド系ポリマーからなる炭素材料前駆体の強度が更に向上するという観点から、２万以上が好ましく、３万以上がより好ましく、４万以上が更に好ましい。
(Acrylamide polymer)
The weight average molecular weight of the acrylamide polymer used in the present invention is 20,000 to 2,000,000. When the weight average molecular weight of the acrylamide polymer exceeds the upper limit, the moldability (spinnability) in film formation, sheet formation, spinning and the like is lowered. On the other hand, when the weight average molecular weight of the acrylamide polymer is less than the lower limit, the strength of the carbon material precursor made of the acrylamide polymer is lowered. Furthermore, the upper limit of the weight average molecular weight of the acrylamide polymer is preferably 1,500,000 or less, more preferably 1,000,000 or less, even more preferably 800,000 or less, from the viewpoint that the moldability (spinnability) is further improved. 500,000 or less is still more preferred, 300,000 or less is particularly preferred, and 200,000 or less is most preferred. Further, the lower limit of the weight average molecular weight of the acrylamide polymer is preferably 20,000 or more, more preferably 30,000 or more, and more preferably 40,000 or more from the viewpoint of further improving the strength of the carbon material precursor made of the acrylamide polymer. Further preferred.
また、本発明に用いられるアクリルアミド系ポリマーは、積分分子量分布曲線において、ポリマー全体に対して、分子量が５０００以下の低分子量成分の占める割合（以下、「低分子量成分含有率」ともいう）が７％以下のものである。アクリルアミド系ポリマーの低分子量成分含有率が前記上限を超えると、酸化性ガス存在下（例えば、空気中）における熱安定性が低く、炭素材料の収率が低下する。さらに、前記アクリルアミド系ポリマーの低分子量成分含有率の上限としては、酸化性ガス存在下における熱安定性が向上し、炭素材料の収率が高くなるという観点から、６％以下が好ましく、５％以下がより好ましく、３％以下が更に好ましく、２．５％以下が特に好ましく、２％以下が最も好ましい。また、前記アクリルアミド系ポリマーの低分子量成分含有率の下限としては０％以上であれば特に制限はないが、成形加工性（紡糸性）が向上するという観点から、０．１％以上が好ましく、０．２％以上がより好ましい。 In addition, the acrylamide polymer used in the present invention has an integral molecular weight distribution curve in which the proportion of low molecular weight components having a molecular weight of 5000 or less (hereinafter also referred to as “low molecular weight component content”) is 7 with respect to the whole polymer. % Or less. If the content of the low molecular weight component of the acrylamide polymer exceeds the upper limit, the thermal stability in the presence of an oxidizing gas (for example, in the air) is low, and the yield of the carbon material is reduced. Furthermore, the upper limit of the content of the low molecular weight component of the acrylamide polymer is preferably 6% or less from the viewpoint of improving the thermal stability in the presence of oxidizing gas and increasing the yield of the carbon material. The following is more preferable, 3% or less is further preferable, 2.5% or less is particularly preferable, and 2% or less is most preferable. Further, the lower limit of the low molecular weight component content of the acrylamide polymer is not particularly limited as long as it is 0% or more, but from the viewpoint of improving the moldability (spinnability), 0.1% or more is preferable, 0.2% or more is more preferable.
なお、本発明において、アクリルアミド系ポリマーの重量平均分子量、積分分子量分布曲線及び低分子量成分の分子量は、ゲルパーミエーションクロマトグラフィーを用いて測定され、標準ポリエチレンオキシド／標準ポリエチレングリコール換算により求められるものである。 In the present invention, the weight average molecular weight, the integral molecular weight distribution curve and the molecular weight of the low molecular weight component of the acrylamide polymer are measured using gel permeation chromatography, and are determined by standard polyethylene oxide / standard polyethylene glycol conversion. is there.
さらに、本発明に用いられるアクリルアミド系ポリマーは、水性溶媒（水、アルコール等、及びこれらの混合溶媒）及び水系混合溶媒（前記水性溶媒と有機溶媒（テトラヒドロフラン等）との混合溶媒）のうちの少なくとも一方に可溶なものであることが好ましい。これにより、炭素材料前駆体を成形する際には、前記水性溶媒又は前記水系混合溶媒を用いた乾式成形（乾式紡糸）、乾湿式成形（乾湿式紡糸）、湿式成形（湿式紡糸）、又はエレクトロスピニングが可能となり、低コストで安全に炭素材料を製造することが可能となる。また、後述する炭素材料前駆体組成物を製造する際に、前記水性溶媒又は前記水系混合溶媒を用いた湿式混合が可能となり、アクリルアミド系ポリマーと後述する添加成分とを均一かつ低コストで安全に混合することが可能となる。さらに、得られた炭素材料前駆体組成物を成形する際には、前記水性溶媒又は前記水系混合溶媒を用いた乾式成形（乾式紡糸）、乾湿式成形（乾湿式紡糸）、湿式成形（湿式紡糸）、又はエレクトロスピニングが可能となり、低コストで安全に炭素材料を製造することが可能となる。なお、前記水系混合溶媒中の有機溶媒の含有量としては、前記水性溶媒に不溶又は難溶なアクリルアミド系ポリマーが有機溶媒を混合することによって溶解する量であれば特に制限はない。また、このようなアクリルアミド系ポリマーの中でも、より低コストで安全に炭素材料前駆体組成物や炭素材料を製造することが可能となるという観点から、前記水性溶媒に可溶なアクリルアミド系ポリマーが好ましく、水に可溶な（水溶性の）アクリルアミド系ポリマーがより好ましい。 Furthermore, the acrylamide polymer used in the present invention is at least one of an aqueous solvent (water, alcohol, etc., and a mixed solvent thereof) and an aqueous mixed solvent (a mixed solvent of the aqueous solvent and an organic solvent (tetrahydrofuran, etc.)). It is preferable that it is soluble in one side. Thus, when the carbon material precursor is molded, dry molding (dry spinning), dry wet molding (dry wet spinning), wet molding (wet spinning), or electroforming using the aqueous solvent or the aqueous mixed solvent. Spinning is possible, and a carbon material can be produced safely at a low cost. In addition, when the carbon material precursor composition described later is manufactured, wet mixing using the aqueous solvent or the aqueous mixed solvent becomes possible, and the acrylamide polymer and the additive component described later can be uniformly and inexpensively and safely. It becomes possible to mix. Further, when the obtained carbon material precursor composition is molded, dry molding (dry spinning), dry wet molding (dry wet spinning), wet molding (wet spinning) using the aqueous solvent or the aqueous mixed solvent. ) Or electrospinning is possible, and a carbon material can be produced safely at low cost. The content of the organic solvent in the aqueous mixed solvent is not particularly limited as long as the acrylamide polymer that is insoluble or hardly soluble in the aqueous solvent is dissolved by mixing the organic solvent. Among such acrylamide polymers, an acrylamide polymer that is soluble in the aqueous solvent is preferable from the viewpoint that a carbon material precursor composition and a carbon material can be produced safely at a lower cost. Water-soluble (water-soluble) acrylamide polymers are more preferable.
このようなアクリルアミド系ポリマーとしては、アクリルアミド系モノマーの単独重合体であっても、アクリルアミド系モノマーと他の重合性モノマーとの共重合体であってもよいが、炭素材料の収率が向上するという観点から、アクリルアミド系モノマーと他の重合性モノマーとの共重合体が好ましい。 Such an acrylamide polymer may be a homopolymer of an acrylamide monomer or a copolymer of an acrylamide monomer and another polymerizable monomer, but the yield of the carbon material is improved. From the viewpoint, a copolymer of an acrylamide monomer and another polymerizable monomer is preferable.
前記アクリルアミド系モノマーと他の重合性モノマーとの共重合体におけるアクリルアミド系モノマー単位の含有量の下限としては、前記共重合体の水性溶媒又は水系混合溶媒に対する可溶性の観点から、５０モル％以上が好ましく、６０モル％以上がより好ましく、７０モル％以上が特に好ましい。また、アクリルアミド系モノマー単位の含有量の上限としては、炭素材料の収率が向上するという観点から、９９．９モル％以下が好ましく、９９モル％以下がより好ましく、９５モル％以下が更に好ましく、９０モル％以下が特に好ましく、８５モル％以下が最も好ましい。 The lower limit of the content of the acrylamide monomer unit in the copolymer of the acrylamide monomer and the other polymerizable monomer is 50 mol% or more from the viewpoint of the solubility of the copolymer in an aqueous solvent or an aqueous mixed solvent. Preferably, 60 mol% or more is more preferable, and 70 mol% or more is particularly preferable. Further, the upper limit of the content of the acrylamide monomer unit is preferably 99.9 mol% or less, more preferably 99 mol% or less, and still more preferably 95 mol% or less, from the viewpoint of improving the yield of the carbon material. 90 mol% or less is particularly preferable, and 85 mol% or less is most preferable.
前記アクリルアミド系モノマーと他の重合性モノマーとの共重合体における他の重合性モノマー単位の含有量の下限としては、炭素材料の収率が向上するという観点から、０．１モル％以上が好ましく、１モル％以上がより好ましく、５モル％以上が更に好ましく、１０モル％以上が特に好ましく、１５モル％以上が最も好ましい。また、他の重合性モノマー単位の含有量の上限としては、前記共重合体の水性溶媒又は水系混合溶媒に対する可溶性の観点から、５０モル％以下が好ましく、４０モル％以下がより好ましく、３０モル％以下が特に好ましい。 The lower limit of the content of the other polymerizable monomer unit in the copolymer of the acrylamide monomer and the other polymerizable monomer is preferably 0.1 mol% or more from the viewpoint of improving the yield of the carbon material. 1 mol% or more is more preferable, 5 mol% or more is further more preferable, 10 mol% or more is especially preferable, and 15 mol% or more is the most preferable. Further, the upper limit of the content of other polymerizable monomer units is preferably 50 mol% or less, more preferably 40 mol% or less, more preferably 30 mol, from the viewpoint of solubility of the copolymer in an aqueous solvent or an aqueous mixed solvent. % Or less is particularly preferable.
前記アクリルアミド系モノマーとしては、例えば、アクリルアミド；Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−ｎ−プロピルアクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−ｎ−ブチルアクリルアミド、Ｎ−ｔｅｒｔ−ブチルアクリルアミド等のＮ−アルキルアクリルアミド；Ｎ−シクロヘキシルアクリルアミド等のＮ−シクロアルキルアクリルアミド；Ｎ，Ｎ−ジメチルアクリルアミド等のジアルキルアクリルアミド；ジメチルアミノエチルアクリルアミド、ジメチルアミノプロピルアクリルアミド等のジアルキルアミノアルキルアクリルアミド；Ｎ−（ヒドロキシメチル）アクリルアミド、Ｎ−（ヒドロキシエチル）アクリルアミド等のヒドロキシアルキルアクリルアミド；Ｎ−フェニルアクリルアミド等のＮ−アリールアクリルアミド；ジアセトンアクリルアミド；Ｎ，Ｎ’−メチレンビスアクリルアミド等のＮ，Ｎ’−アルキレンビスアクリルアミド；メタクリルアミド；Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド、Ｎ−ｎ−プロピルメタクリルアミド、Ｎ−イソプロピルメタクリルアミド、Ｎ−ｎ−ブチルメタクリルアミド、Ｎ−ｔｅｒｔ−ブチルメタクリルアミド等のＮ−アルキルメタクリルアミド；Ｎ−シクロヘキシルメタクリルアミド等のＮ−シクロアルキルメタクリルアミド；Ｎ，Ｎ−ジメチルメタクリルアミド等のジアルキルメタクリルアミド；ジメチルアミノエチルメタクリルアミド、ジメチルアミノプロピルメタクリルアミド等のジアルキルアミノアルキルメタクリルアミド；Ｎ−（ヒドロキシメチル）メタクリルアミド、Ｎ−（ヒドロキシエチル）メタクリルアミド等のヒドロキシアルキルメタクリルアミド；Ｎ−フェニルメタクリルアミド等のＮ−アリールメタクリルアミド；ジアセトンメタクリルアミド；Ｎ，Ｎ’−メチレンビスメタクリルアミド等のＮ，Ｎ’−アルキレンビスメタクリルアミドが挙げられる。これらのアクリルアミド系モノマーは１種を単独で使用しても２種以上を併用してもよい。また、これらのアクリルアミド系モノマーの中でも、水性溶媒又は水系混合溶媒への溶解性が高いという観点から、アクリルアミド、Ｎ−アルキルアクリルアミド、ジアルキルアクリルアミド、メタクリルアミド、Ｎ−アルキルメタクリルアミド、ジアルキルメタクリルアミドが好ましく、アクリルアミドが特に好ましい。 Examples of the acrylamide monomer include N-methylacrylamide, N-ethylacrylamide, Nn-propylacrylamide, N-isopropylacrylamide, Nn-butylacrylamide, N-tert-butylacrylamide, and the like. Alkyl acrylamides; N-cycloalkyl acrylamides such as N-cyclohexyl acrylamide; dialkyl acrylamides such as N, N-dimethyl acrylamide; dialkylaminoalkyl acrylamides such as dimethylaminoethyl acrylamide and dimethylaminopropyl acrylamide; N- (hydroxymethyl) acrylamide; Hydroxyalkyl acrylamides such as N- (hydroxyethyl) acrylamide; -Aryl acrylamide; diacetone acrylamide; N, N'-alkylene bisacrylamide such as N, N'-methylene bisacrylamide; methacrylamide; N-methyl methacrylamide, N-ethyl methacrylamide, Nn-propyl methacrylamide, N-alkyl methacrylamide such as N-isopropyl methacrylamide, Nn-butyl methacrylamide, N-tert-butyl methacrylamide; N-cycloalkyl methacrylamide such as N-cyclohexyl methacrylamide; N, N-dimethyl methacrylamide Dialkyl methacrylamide such as dimethylaminoethyl methacrylamide, dimethylaminopropyl methacrylamide and the like; N- (hydroxymethyl) meta Hydroxyalkyl methacrylamide such as rilamide, N- (hydroxyethyl) methacrylamide; N-aryl methacrylamide such as N-phenylmethacrylamide; diacetone methacrylamide; N, N ′ such as N, N′-methylenebismethacrylamide -Alkylenebismethacrylamide. These acrylamide monomers may be used alone or in combination of two or more. Among these acrylamide monomers, acrylamide, N-alkyl acrylamide, dialkyl acrylamide, methacrylamide, N-alkyl methacrylamide, and dialkyl methacrylamide are preferable from the viewpoint of high solubility in an aqueous solvent or an aqueous mixed solvent. Acrylamide is particularly preferred.
前記他の重合性モノマーとしては、例えば、シアン化ビニル系モノマー、不飽和カルボン酸及びその塩、不飽和カルボン酸無水物、不飽和カルボン酸エステル、ビニル系モノマー、オレフィン系モノマーが挙げられる。前記シアン化ビニル系モノマーとしては、アクリロニトリル、メタクリロニトリル、２−ヒドロキシエチルアクリロニトリル、クロロアクリロニトリル、クロロメタクリロニトリル、メトキシアクリロニトリル、メトキシメタクリロニトリル等が挙げられる。前記不飽和カルボン酸としては、アクリル酸、メタクリル酸、イタコン酸等が挙げられ、前記不飽和カルボン酸無水物としては、無水マレイン酸、イタコン酸無水物等が挙げられ、前記不飽和カルボン酸エステルとしては、アクリル酸メチル、メタクリル酸メチル、アクリル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキシエチル等が挙げられ、前記ビニル系モノマーとしては、スチレン、α−メチルスチレン、塩化ビニル、ビニルアルコール等が挙げられ、前記オレフィン系モノマーとしては、エチレン、プロピレン等が挙げられる。これらの他の重合性モノマーは１種を単独で使用しても２種以上を併用してもよい。また、これらの他の重合性モノマーの中でも、炭素材料前駆体の成形加工性（紡糸性）が向上し、炭素材料の収率が向上するという観点からは、シアン化ビニル系モノマーが好ましく、アクリロニトリルが特に好ましく、前記共重合体の水性溶媒又は水系混合溶媒に対する可溶性の観点からは、不飽和カルボン酸及びその塩が好ましい。 Examples of the other polymerizable monomers include vinyl cyanide monomers, unsaturated carboxylic acids and salts thereof, unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid esters, vinyl monomers, and olefin monomers. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, 2-hydroxyethylacrylonitrile, chloroacrylonitrile, chloromethacrylonitrile, methoxyacrylonitrile, methoxymethacrylonitrile and the like. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, and itaconic acid. Examples of the unsaturated carboxylic acid anhydride include maleic anhydride and itaconic anhydride. The unsaturated carboxylic acid ester. Examples include methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and the vinyl monomers include styrene, α-methylstyrene, vinyl chloride, vinyl alcohol, and the like. Examples of the olefin monomer include ethylene and propylene. These other polymerizable monomers may be used alone or in combination of two or more. Among these other polymerizable monomers, vinyl cyanide monomers are preferred from the viewpoint of improving the molding processability (spinnability) of the carbon material precursor and improving the yield of the carbon material, and acrylonitrile. Is particularly preferable, and from the viewpoint of solubility of the copolymer in an aqueous solvent or an aqueous mixed solvent, an unsaturated carboxylic acid and a salt thereof are preferable.
このような本発明の炭素材料前駆体を製造する方法としては、ラジカル重合、カチオン重合、アニオン重合、リビングラジカル重合等の公知の重合反応を、溶液重合、懸濁重合、沈殿重合、分散重合、乳化重合（例えば、逆相乳化重合）等の重合方法を採用することができる。前記重合反応の中でも、得られるアクリルアミド系ポリマーの低分子量成分含有率を小さくでき、炭素材料の収率が向上し、さらに、炭素材料前駆体を低コストで製造できるという観点から、ラジカル重合が好ましい。また、溶液重合を採用する場合、溶媒としては、原料のモノマー及び得られるアクリルアミド系ポリマーが溶解するものを使用することが好ましく、低コストで安全に製造できるという観点から、前記水性溶媒（水、アルコール等、及びこれらの混合溶媒等）又は前記水系混合溶媒（前記水性溶媒と有機溶媒（テトラヒドロフラン等）との混合溶媒）を使用することがより好ましく、前記水性溶媒を使用することが特に好ましく、水を使用することが最も好ましい。 As a method for producing such a carbon material precursor of the present invention, known polymerization reactions such as radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization, etc., solution polymerization, suspension polymerization, precipitation polymerization, dispersion polymerization, A polymerization method such as emulsion polymerization (for example, reverse phase emulsion polymerization) can be employed. Among the above polymerization reactions, radical polymerization is preferable from the viewpoint that the low molecular weight component content of the obtained acrylamide polymer can be reduced, the yield of the carbon material is improved, and further, the carbon material precursor can be produced at low cost. . In addition, when employing solution polymerization, it is preferable to use a solvent in which the raw material monomer and the acrylamide polymer to be obtained are dissolved, and from the viewpoint that it can be safely produced at low cost, the aqueous solvent (water, Alcohol or the like, and a mixed solvent thereof) or the aqueous mixed solvent (a mixed solvent of the aqueous solvent and an organic solvent (tetrahydrofuran or the like)) is more preferable, and the aqueous solvent is particularly preferable. Most preferably, water is used.
前記ラジカル重合においては、重合開始剤として、アゾビスイソブチロニトリル、過酸化ベンゾイル、４，４’−アゾビス（４−シアノ吉草酸）、過硫酸アンモニウム、過硫酸カリウム等の従来公知のラジカル重合開始剤を使用することができるが、溶媒として前記水性溶媒又は前記水系混合溶媒を使用する場合には、４，４’−アゾビス（４−シアノ吉草酸）、過硫酸アンモニウム、過硫酸カリウム等の前記水性溶媒又は前記水系混合溶媒（好ましくは前記水性溶媒、より好ましくは水）に可溶なラジカル重合開始剤が好ましい。また、得られるアクリルアミド系ポリマーの低分子量成分含有率を小さくでき、炭素材料の収率が向上するという観点から、前記重合開始剤に代えて又は加えて、テトラメチルエチレンジアミン等の従来公知の重合促進剤やｎ−ドデシルメルカプタン等のアルキルメルカプタン等の分子量調節剤を用いることが好ましく、前記前記重合開始剤と前記重合促進剤とを併用することが好ましく、過硫酸アンモニウムとテトラメチルエチレンジアミンとを併用することが特に好ましい。 In the radical polymerization, conventionally known radical polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, 4,4′-azobis (4-cyanovaleric acid), ammonium persulfate, and potassium persulfate are used as polymerization initiators. However, when the aqueous solvent or the aqueous mixed solvent is used as a solvent, the aqueous solution such as 4,4′-azobis (4-cyanovaleric acid), ammonium persulfate, potassium persulfate, etc. A radical polymerization initiator that is soluble in the solvent or the aqueous mixed solvent (preferably the aqueous solvent, more preferably water) is preferable. Further, from the viewpoint of reducing the content of low molecular weight components of the obtained acrylamide polymer and improving the yield of the carbon material, instead of or in addition to the polymerization initiator, conventionally known polymerization acceleration such as tetramethylethylenediamine It is preferable to use a molecular weight regulator such as an alkyl mercaptan such as an agent or n-dodecyl mercaptan, preferably the polymerization initiator and the polymerization accelerator are used in combination, and ammonium persulfate and tetramethylethylenediamine are used in combination. Is particularly preferred.
重合開始剤を添加する際の温度としては特に制限はないが、得られるアクリルアミド系ポリマーの低分子量成分含有率を小さくでき、炭素材料の収率が向上するという観点から、３５℃以上が好ましく、４０℃以上がより好ましく、４５℃以上が更に好ましく、５０℃以上が特に好ましく、５５℃以上が最も好ましい。また、前記重合反応の温度としては特に制限はないが、低分子量成分の生成が抑制され、得られるアクリルアミド系ポリマーの低分子量成分含有率を小さくでき、炭素材料の収率が向上するという観点から、５０℃以上が好ましく、６０℃以上がより好ましく、７０℃以上が特に好ましく、７５℃以上が最も好ましい。 The temperature at which the polymerization initiator is added is not particularly limited, but it is preferably 35 ° C. or higher from the viewpoint that the content of low molecular weight components of the obtained acrylamide polymer can be reduced and the yield of the carbon material is improved. 40 ° C. or higher is more preferable, 45 ° C. or higher is further preferable, 50 ° C. or higher is particularly preferable, and 55 ° C. or higher is most preferable. Further, the temperature of the polymerization reaction is not particularly limited, but from the viewpoint that the generation of low molecular weight components is suppressed, the content of low molecular weight components of the resulting acrylamide polymer can be reduced, and the yield of the carbon material is improved. 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and most preferably 75 ° C. or higher.
また、本発明の炭素材料前駆体を製造する際には、重合反応後のアクリルアミド系ポリマーを溶媒を用いて、分子量が５０００以下の低分子量成分を抽出除去してもよい。これにより、アクリルアミド系ポリマーの低分子量成分含有率を小さくすることができ、炭素材料の収率が向上する。抽出除去に用いられる溶媒としては特に制限はないが、例えば、メタノール、エタノール、プロパノール、イソプロパノール等のアルコール、ジメチルスルホキシド、ジメチルアセトアミド等の有機溶媒が挙げられる。また、抽出除去の際の温度としては特に制限はないが、低分子量成分が抽出除去されやすいという観点から、３０℃以上が好ましく、４０℃以上がより好ましく、５０℃以上が更に好ましく、６０℃以上が特に好ましい。 Further, when the carbon material precursor of the present invention is produced, a low molecular weight component having a molecular weight of 5000 or less may be extracted and removed using a solvent for the acrylamide polymer after the polymerization reaction. Thereby, the low molecular weight component content of the acrylamide polymer can be reduced, and the yield of the carbon material is improved. Although there is no restriction | limiting in particular as a solvent used for extraction removal, For example, organic solvents, such as alcohol, such as methanol, ethanol, propanol, and isopropanol, dimethylsulfoxide, and dimethylacetamide, are mentioned. The temperature at the time of extraction removal is not particularly limited, but is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, still more preferably 50 ° C. or higher, and 60 ° C. from the viewpoint that low molecular weight components are easily extracted and removed. The above is particularly preferable.
〔炭素材料前駆体組成物〕
次に、本発明の炭素材料前駆体組成物について説明する。本発明の炭素材料前駆体組成物は、前記本発明の炭素材料前駆体と、酸及びその塩からなる群から選択される少なくとも１種の添加成分とを含有するものである。本発明の炭素材料前駆体に、酸及びその塩からなる群から選択される少なくとも１種の添加成分を添加することによって、炭素材料の収率が更に向上する。
[Carbon material precursor composition]
Next, the carbon material precursor composition of the present invention will be described. The carbon material precursor composition of the present invention contains the carbon material precursor of the present invention and at least one additive component selected from the group consisting of acids and salts thereof. By adding at least one additive component selected from the group consisting of an acid and a salt thereof to the carbon material precursor of the present invention, the yield of the carbon material is further improved.
本発明の炭素材料前駆体組成物において、このような添加成分の含有量としては、炭素材料の収率が更に向上するという観点から、前記炭素材料前駆体１００質量部に対して０．１〜１００質量部が好ましく、０．２〜５０質量部がより好ましく、０．３〜４０質量部が更に好ましく、０．５〜３０質量部が特に好ましく、１〜２０質量部が最も好ましい。 In the carbon material precursor composition of the present invention, the content of such an additive component is 0.1 to 100 parts by mass with respect to 100 parts by mass of the carbon material precursor from the viewpoint of further improving the yield of the carbon material. 100 mass parts is preferable, 0.2-50 mass parts is more preferable, 0.3-40 mass parts is still more preferable, 0.5-30 mass parts is especially preferable, and 1-20 mass parts is the most preferable.
前記酸としては、リン酸、ポリリン酸、ホウ酸、ポリホウ酸、硫酸、硝酸、炭酸、塩酸等の無機酸、シュウ酸、クエン酸、スルホン酸、酢酸等の有機酸が挙げられる。また、このような酸の塩としては、金属塩（例えば、ナトリウム塩、カリウム塩）、アンモニウム塩、アミン塩等が挙げられ、アンモニウム塩、アミン塩が好ましく、アンモニウム塩がより好ましい。特に、これらの添加成分のうち、炭素材料の収率が更に向上するという観点から、リン酸、ポリリン酸、ホウ酸、ポリホウ酸、硫酸、及びこれらのアンモニウム塩が好ましく、リン酸、ポリリン酸、及びこれらのアンモニウム塩が特に好ましい。 Examples of the acid include inorganic acids such as phosphoric acid, polyphosphoric acid, boric acid, polyboric acid, sulfuric acid, nitric acid, carbonic acid, and hydrochloric acid, and organic acids such as oxalic acid, citric acid, sulfonic acid, and acetic acid. Examples of such acid salts include metal salts (for example, sodium salts and potassium salts), ammonium salts, and amine salts. Ammonium salts and amine salts are preferable, and ammonium salts are more preferable. Among these additive components, phosphoric acid, polyphosphoric acid, boric acid, polyboric acid, sulfuric acid, and ammonium salts thereof are preferred from the viewpoint of further improving the yield of the carbon material, and phosphoric acid, polyphosphoric acid, And their ammonium salts are particularly preferred.
前記添加成分は、前記水性溶媒及び前記水系混合溶媒のうちの少なくとも一方（より好ましくは前記水性溶媒、特に好ましくは水）に可溶なものであることが好ましい。これにより、炭素材料前駆体組成物を製造する際に、前記水性溶媒又は前記水系混合溶媒を用いた湿式混合が可能となり、前記アクリルアミド系ポリマーと前記添加成分とを均一かつ低コストで安全に混合することが可能となる。また、得られた炭素材料前駆体組成物を成形する際には、前記水性溶媒又は前記水系混合溶媒を用いた乾式成形（乾式紡糸）、乾湿式成形（乾湿式紡糸）、湿式成形（湿式紡糸）、又はエレクトロスピニングが可能となり、低コストで安全に炭素材料を製造することが可能となる。 The additive component is preferably soluble in at least one of the aqueous solvent and the aqueous mixed solvent (more preferably the aqueous solvent, particularly preferably water). As a result, when the carbon material precursor composition is produced, wet mixing using the aqueous solvent or the aqueous mixed solvent becomes possible, and the acrylamide polymer and the additive component are uniformly and safely mixed at a low cost. It becomes possible to do. Further, when molding the obtained carbon material precursor composition, dry molding (dry spinning), dry wet molding (dry wet spinning), wet molding (wet spinning) using the aqueous solvent or the aqueous mixed solvent. ) Or electrospinning is possible, and a carbon material can be produced safely at low cost.
このような本発明の炭素材料前駆体組成物を製造する方法としては、溶融状態の前記炭素材料前駆体に前記添加成分を直接混合する方法（溶融混合）、前記炭素材料前駆体と前記添加成分とをドライブレンドする方法（乾式混合）、前記添加成分を含有する水性溶液又は水系混合溶液、或いは前記炭素材料前駆体は完全溶解していないが前記添加成分は溶解している溶液に所望の形状（例えば、フィルム状、シート状、繊維状）に成形した前記炭素材料前駆体を浸漬したり、通過させたりする方法等を採用することも可能であるが、使用する前記炭素材料前駆体及び前記添加成分が前記水性溶媒又は前記水系混合溶媒に可溶な場合には、前記炭素材料前駆体と前記添加成分とを均一に混合することができるという観点から、前記炭素材料前駆体と前記添加成分とを前記水性溶媒又は前記水系混合溶媒中で混合する方法（湿式混合）が好ましい。また、湿式混合としては、前記炭素材料前駆体の製造に際し、前述の重合を前記水性溶媒中又は前記水系混合溶媒中で行なった場合に、重合後等に前記添加成分を混合する方法も採用することができる。さらに、得られる溶液から前記溶媒を除去することによって本発明の炭素材料前駆体組成物を回収し、これを後述する炭素材料の製造に用いることができるほか、前記溶媒を除去することなく、得られる溶液をそのまま後述する炭素材料の製造に用いることもできる。また、前記湿式混合においては、より低コストで安全に炭素材料前駆体組成物を製造できるという観点から、溶媒として前記水性溶媒を使用することが好ましく、水を使用することがより好ましい。さらに、前記溶媒を除去する方法としては特に制限はなく、減圧留去、再沈殿、熱風乾燥、真空乾燥、凍結乾燥等の公知の方法のうちの少なくとも１つの方法を採用することができる。 As a method for producing such a carbon material precursor composition of the present invention, a method of directly mixing the additive component into the carbon material precursor in a molten state (melt mixing), the carbon material precursor and the additive component In an aqueous solution or an aqueous mixed solution containing the additive component, or a solution in which the carbon material precursor is not completely dissolved but the additive component is dissolved in a desired shape. Although it is possible to employ a method of immersing or passing the carbon material precursor formed into (for example, a film shape, a sheet shape, or a fiber shape), the carbon material precursor to be used and the In the case where the additive component is soluble in the aqueous solvent or the water-based mixed solvent, the carbon material precursor can be uniformly mixed with the carbon material precursor and the additive component. A method of mixing the additional component in the aqueous solvent or the aqueous solvent mixture (wet mixing) is preferred. In addition, as the wet mixing, a method of mixing the additive components after polymerization or the like when the above-described polymerization is performed in the aqueous solvent or the aqueous mixed solvent in the production of the carbon material precursor is also adopted. be able to. Furthermore, the carbon material precursor composition of the present invention can be recovered by removing the solvent from the resulting solution, which can be used for the production of the carbon material described later, and can be obtained without removing the solvent. The obtained solution can be used as it is for the production of the carbon material described later. Moreover, in the said wet mixing, it is preferable to use the said aqueous solvent as a solvent from a viewpoint that a carbon material precursor composition can be manufactured safely at lower cost, and it is more preferable to use water. Furthermore, there is no restriction | limiting in particular as the method of removing the said solvent, At least 1 method of well-known methods, such as distillation under reduced pressure, reprecipitation, hot air drying, vacuum drying, freeze drying, can be employ | adopted.
〔炭素材料の製造方法〕
次に、本発明の炭素材料の製造方法について説明する。本発明の炭素材料の製造方法は、前記本発明の炭素材料前駆体又は前記本発明の炭素材料前駆体組成物に不活性雰囲気下（窒素、アルゴン、ヘリウム等の不活性ガス中）で加熱処理（炭化処理）を施す方法である。これにより、炭素材料前駆体が炭化し、所望の炭素材料が得られる。また、前記本発明の炭素材料前駆体又は前記本発明の炭素材料前駆体組成物に加熱処理を施しても急激な発熱が起こらず、ポリアクリルアミド系ポリマーが熱分解されないため、本発明の炭素材料の製造方法においては、炭化処理時の加熱温度（炭化処理温度）までの昇温時間を短くすることができ、効率的に炭素材料を製造することが可能となる。なお、本発明にかかる「炭化処理」には、一般的に、不活性ガス雰囲気下、２０００〜３０００℃で加熱することによって行われる「黒鉛化」を含んでいてもよい。
[Method for producing carbon material]
Next, the manufacturing method of the carbon material of this invention is demonstrated. The method for producing a carbon material according to the present invention comprises subjecting the carbon material precursor of the present invention or the carbon material precursor composition of the present invention to a heat treatment in an inert atmosphere (in an inert gas such as nitrogen, argon or helium). (Carbonization treatment). Thereby, a carbon material precursor carbonizes and a desired carbon material is obtained. In addition, since the carbon material precursor of the present invention or the carbon material precursor composition of the present invention is subjected to a heat treatment, no rapid heat generation occurs and the polyacrylamide polymer is not thermally decomposed. In this manufacturing method, it is possible to shorten the temperature raising time to the heating temperature (carbonization temperature) during carbonization, and it is possible to efficiently manufacture the carbon material. The “carbonization treatment” according to the present invention may generally include “graphitization” performed by heating at 2000 to 3000 ° C. in an inert gas atmosphere.
前記炭化処理温度としては、５００℃以上が好ましく、１０００℃以上がより好ましい。また、炭化処理温度の上限としては、３０００℃以下が好ましく、２０００℃以下がより好ましい。また、前記炭化処理においては、例えば、先に１０００℃未満の温度で加熱処理を行なった後、１０００℃以上の温度で加熱処理を行うといったように、複数回の加熱処理を行うこともできる。さらに、炭化処理における加熱時間（炭化処理時間）としては特に制限はないが、１〜６０分間が好ましく、１〜３０分間がより好ましい。 The carbonization temperature is preferably 500 ° C. or higher, and more preferably 1000 ° C. or higher. Moreover, as an upper limit of carbonization temperature, 3000 degrees C or less is preferable and 2000 degrees C or less is more preferable. Further, in the carbonization treatment, for example, the heat treatment may be performed a plurality of times such as the heat treatment is first performed at a temperature of less than 1000 ° C. and then the heat treatment is performed at a temperature of 1000 ° C. or higher. Furthermore, although there is no restriction | limiting in particular as the heating time (carbonization time) in carbonization, 1 to 60 minutes are preferable and 1 to 30 minutes are more preferable.
また、本発明の炭素材料の製造方法においては、前記炭化処理の前に、必要に応じて、前記本発明の炭素材料前駆体又は前記本発明の炭素材料前駆体組成物に酸化性雰囲気下（例えば、空気中）で加熱処理（耐炎化処理）を施してもよい。前記本発明の炭素材料前駆体は、低分子量成分の含有率が小さいアクリルアミド系ポリマーからなるものであるため、耐炎化処理において熱分解されにくく、また、炭素材料前駆体を構成するアクリルアミド系ポリマーの構造が耐熱性の高い構造に変換されるため、高い耐炎化収率を示す。さらに、耐炎化処理が施された炭素材料前駆体（耐炎化物）は、耐熱性の高い構造を有しているため、高い炭化収率を示し、最終的な炭素材料の収率が向上する。特に、前記炭素材料前駆体組成物においては、添加成分である酸やその塩の触媒作用により、アクリルアミド系ポリマーの脱アンモニア反応や脱水反応が促進されるため、分子内に環状構造（イミド環構造）が形成されやすく、アクリルアミド系ポリマーの構造が耐熱性の高い構造に変換されやすいため、炭素材料前駆体の耐炎化収率や耐炎化物の炭化収率が更に高くなり、最終的な炭素材料の収率も更に向上する。また、前記本発明の炭素材料前駆体又は前記本発明の炭素材料前駆体組成物に加熱処理を施しても急激な発熱が起こらず、加熱炉内の熱制御が容易となるほか、ポリアクリルアミド系ポリマーの熱分解が大きく抑制されるため、本発明の炭素材料の製造方法においては、多量のポリアクリルアミド系ポリマーを同時に耐炎化処理することが可能となり、かつ、耐炎化処理時の加熱温度（耐炎化処理温度）までの昇温時間を短くすることができ、効率的に炭素材料を製造することが可能となる。 In the method for producing a carbon material of the present invention, the carbon material precursor of the present invention or the carbon material precursor composition of the present invention is subjected to an oxidizing atmosphere (if necessary) before the carbonization treatment. For example, the heat treatment (flame resistance treatment) may be performed in the air. Since the carbon material precursor of the present invention is composed of an acrylamide polymer having a low content of low molecular weight components, it is difficult to be thermally decomposed in the flameproofing treatment, and the acrylamide polymer that constitutes the carbon material precursor. Since the structure is converted into a structure having high heat resistance, a high flameproofing yield is exhibited. Furthermore, since the carbon material precursor (flame-resistant product) that has been subjected to flameproofing treatment has a structure with high heat resistance, it exhibits a high carbonization yield and improves the yield of the final carbon material. Particularly, in the carbon material precursor composition, the deammonification reaction or dehydration reaction of the acrylamide polymer is promoted by the catalytic action of the acid or salt as an additive component. ), And the structure of the acrylamide polymer is easily converted to a structure with high heat resistance, so that the yield of flameproofing of the carbon material precursor and the carbonization yield of the flameproofed product are further increased, and the final carbon material The yield is further improved. In addition, when the carbon material precursor of the present invention or the carbon material precursor composition of the present invention is subjected to a heat treatment, rapid heat generation does not occur, and heat control in the heating furnace is facilitated. Since the thermal decomposition of the polymer is greatly suppressed, in the method for producing a carbon material of the present invention, a large amount of polyacrylamide polymer can be subjected to a flameproofing treatment at the same time, and the heating temperature (flameproofing) The temperature rise time until the (chemical treatment temperature) can be shortened, and the carbon material can be efficiently produced.
前記耐炎化処理温度としては、１５０〜５００℃が好ましく、２００〜４５０℃がより好ましく、２４０〜４２０℃が更に好ましく、２８０〜４１０℃がまた更に好ましく、３１０〜４００℃が特に好ましく、３２０〜３９０℃が最も好ましい。また、耐炎化処理における加熱時間（耐炎化処理時間）としては特に制限はなく、長時間（例えば１時間超）の加熱も可能であるが、コスト低減の観点から１〜６０分間が好ましい。 The flameproofing treatment temperature is preferably 150 to 500 ° C, more preferably 200 to 450 ° C, further preferably 240 to 420 ° C, still more preferably 280 to 410 ° C, particularly preferably 310 to 400 ° C, 320 to Most preferred is 390 ° C. The heating time in the flameproofing treatment (flameproofing treatment time) is not particularly limited, and heating for a long time (for example, more than 1 hour) is possible, but 1 to 60 minutes is preferable from the viewpoint of cost reduction.
また、本発明の炭素材料の製造方法においては、耐炎化処理の前に（耐炎化処理を施さなかった場合には炭化処理の前に）、使用する炭素材料前駆体又は炭素材料前駆体組成物を予め所望の形状（例えば、フィルム状、シート状、繊維状）に成形加工することが好ましい。このとき、本発明の炭素材料前駆体及び炭素材料前駆体組成物が成形加工性に優れたものであるため、炭素材料前駆体又は炭素材料前駆体組成物をそのまま加圧成形したり、溶融状態の炭素材料前駆体又は炭素材料前駆体組成物を用いて溶融成形（例えば、溶融キャスト成形、溶融押出成形、射出成形、溶融紡糸、スパンボンド、メルトブローン、遠心紡糸）してもよいが、本発明の炭素材料前駆体又は炭素材料前駆体組成物が前記水性溶媒又は前記水系混合溶媒に可溶な場合には、成形加工性が更に高まるという観点から、前記炭素材料前駆体又は前記炭素材料前駆体組成物を前記水性溶媒又は前記水系混合溶媒に溶解し、得られた水性溶液又は水系混合溶液を用いて成形すること、或いは、前述の重合後の炭素材料前駆体の溶液又は前述の湿式混合で得られる炭素材料前駆体組成物の溶液をそのまま若しくは所望の濃度に調整した後、成形すること、が好ましい。このような成形方法としては、溶液キャスト成形、湿式成形、乾式紡糸、湿式紡糸、乾湿式紡糸、ゲル紡糸、フラッシュ紡糸、又はエレクトロスピニングを行うことが好ましい。これにより、所望の形状の炭素材料前駆体又は炭素材料前駆体組成物を低コストで安全に製造することができる。また、より低コストで安全に炭素材料を製造することができるという観点から、溶媒として前記水性溶媒を使用することがより好ましく、水を使用することが特に好ましい。このように予め所望の形状に成形加工した炭素材料前駆体又は炭素材料前駆体組成物を用いることによって、所望の形状の炭素材料（例えば、炭素フィルム、炭素シート、炭素繊維）を製造することができる。 Further, in the method for producing a carbon material of the present invention, the carbon material precursor or the carbon material precursor composition to be used is used before the flameproofing treatment (before the carbonization treatment if no flameproofing treatment is performed). It is preferable to mold the material into a desired shape (for example, a film shape, a sheet shape, or a fiber shape) in advance. At this time, since the carbon material precursor and the carbon material precursor composition of the present invention are excellent in molding processability, the carbon material precursor or the carbon material precursor composition is directly pressure-molded or melted. The carbon material precursor or the carbon material precursor composition may be melt-molded (for example, melt cast molding, melt extrusion molding, injection molding, melt spinning, spunbond, meltblown, centrifugal spinning). When the carbon material precursor or the carbon material precursor composition is soluble in the aqueous solvent or the aqueous mixed solvent, the carbon material precursor or the carbon material precursor is used from the viewpoint of further improving the molding processability. The composition is dissolved in the aqueous solvent or the aqueous mixed solvent and molded using the obtained aqueous solution or aqueous mixed solution, or the solution of the carbon material precursor after the polymerization or the aforementioned After adjusting to it is or desired concentration solution of the carbon material precursor composition obtained by wet mixing, be molded, preferably. As such a molding method, it is preferable to perform solution cast molding, wet molding, dry spinning, wet spinning, dry wet spinning, gel spinning, flash spinning, or electrospinning. Thereby, a carbon material precursor or a carbon material precursor composition having a desired shape can be safely produced at a low cost. Further, from the viewpoint that the carbon material can be produced safely at a lower cost, it is more preferable to use the aqueous solvent as a solvent, and it is particularly preferable to use water. By using a carbon material precursor or a carbon material precursor composition that has been molded and processed into a desired shape in advance, a carbon material having a desired shape (for example, a carbon film, a carbon sheet, or a carbon fiber) can be produced. it can.
また、前記水性溶液又は前記水系混合溶液における前記炭素材料前駆体又は前記炭素材料前駆体組成物の濃度としては特に制限はないが、生産性向上とコスト低減の観点から、２０質量％以上の高濃度が好ましい。なお、前記炭素材料前駆体又は前記炭素材料前駆体組成物の濃度が高くなりすぎると、前記水性溶液又は前記水系混合溶液の粘度が高くなり、成形加工性が低下するため、前記水性溶液又は前記水系混合溶液の濃度を、粘度を指標として、成形加工が可能の濃度に調整することが好ましい。 Further, the concentration of the carbon material precursor or the carbon material precursor composition in the aqueous solution or the aqueous mixed solution is not particularly limited. However, from the viewpoint of productivity improvement and cost reduction, a high concentration of 20% by mass or more. Concentration is preferred. In addition, when the concentration of the carbon material precursor or the carbon material precursor composition is too high, the viscosity of the aqueous solution or the aqueous mixed solution is increased, and the molding processability is reduced. It is preferable to adjust the concentration of the aqueous mixed solution to a concentration at which molding can be performed using the viscosity as an index.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、実施例で使用した各アクリルアミド系ポリマーの合成方法、及びそれらの分子量の測定方法を以下に示す。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, the synthesis | combining method of each acrylamide type polymer used in the Example, and the measuring method of those molecular weight are shown below.
（合成例１）
アクリルアミド（ＡＡｍ、和光純薬工業株式会社製）１２．８ｇ（０．１８ｍｏｌ）をイオン交換水１８０ｍｌに溶解し、得られた水溶液にテトラメチルエチレンジアミン１．３５ｍｌ（０．００９ｍｏｌ）を添加して、窒素雰囲気下、撹拌しながら５０℃まで昇温した。次いで、過硫酸アンモニウム０．２５２ｇ（０．００１１ｍｏｌ）を添加した後、６０℃で３時間重合反応を行なった。得られた水溶液をメタノール中に投入して重合物を析出させ、これを回収して真空乾燥させることにより、水溶性のポリアクリルアミド（ＰＡＡｍ）を得た。
(Synthesis Example 1)
Acrylamide (AAm, manufactured by Wako Pure Chemical Industries, Ltd.) 12.8 g (0.18 mol) was dissolved in 180 ml of ion-exchanged water, and 1.35 ml (0.009 mol) of tetramethylethylenediamine was added to the resulting aqueous solution. The temperature was raised to 50 ° C. with stirring in a nitrogen atmosphere. Next, after adding 0.252 g (0.0011 mol) of ammonium persulfate, a polymerization reaction was carried out at 60 ° C. for 3 hours. The obtained aqueous solution was poured into methanol to precipitate a polymer, which was recovered and vacuum dried to obtain water-soluble polyacrylamide (PAAm).
（合成例２）
アクリルアミド（ＡＡｍ、和光純薬工業株式会社製）１２．８ｇ（０．１８ｍｏｌ）をイオン交換水１８０ｍｌに溶解し、得られた水溶液にテトラメチルエチレンジアミン１．３５ｍｌ（０．００９ｍｏｌ）を添加して、窒素雰囲気下、撹拌しながら６０℃まで昇温した。次いで、過硫酸アンモニウム０．１５２ｇ（０．０００６７ｍｏｌ）を添加した後、８０℃で２時間重合反応を行い、さらに、９０℃まで昇温した後、９０℃で１時間重合反応を行なった。得られた水溶液をメタノール中に投入して重合物を析出させ、これを回収して真空乾燥させることにより、水溶性のポリアクリルアミド（ＰＡＡｍ）を得た。
(Synthesis Example 2)
Acrylamide (AAm, manufactured by Wako Pure Chemical Industries, Ltd.) 12.8 g (0.18 mol) was dissolved in 180 ml of ion-exchanged water, and 1.35 ml (0.009 mol) of tetramethylethylenediamine was added to the resulting aqueous solution. The temperature was raised to 60 ° C. with stirring in a nitrogen atmosphere. Next, 0.152 g (0.00067 mol) of ammonium persulfate was added, and then a polymerization reaction was performed at 80 ° C. for 2 hours. After the temperature was raised to 90 ° C., the polymerization reaction was performed at 90 ° C. for 1 hour. The obtained aqueous solution was poured into methanol to precipitate a polymer, which was recovered and vacuum dried to obtain water-soluble polyacrylamide (PAAm).
（合成例３）
アクリルアミド（ＡＡｍ、和光純薬工業株式会社製）９６．０ｇ（１．３５ｍｏｌ）及びアクリロニトリル（ＡＮ）２３．９ｇ（０．４５ｍｏｌ）をイオン交換水４８０ｍｌに溶解し、得られた水溶液にテトラメチルエチレンジアミン６．７５ｍｌ（０．０４５ｍｏｌ）を添加して、窒素雰囲気下、撹拌しながら５０℃まで昇温した。次いで、過硫酸アンモニウム１．５２ｇ（０．００６７ｍｏｌ）を添加した後、５０℃で４時間重合反応を行い、さらに、９０℃まで昇温した後、９０℃で１時間重合反応を行なった。得られた水溶液をメタノール中に投入して共重合物を析出させ、これを回収して真空乾燥させることにより、水溶性のアクリルアミド／アクリロニトリル共重合体（ＡＡｍ／ＡＮ共重合体）を得た。
(Synthesis Example 3)
Acrylamide (AAm, manufactured by Wako Pure Chemical Industries, Ltd.) 96.0 g (1.35 mol) and acrylonitrile (AN) 23.9 g (0.45 mol) were dissolved in 480 ml of ion-exchanged water, and tetramethylethylenediamine was added to the resulting aqueous solution. 6.75 ml (0.045 mol) was added and the temperature was raised to 50 ° C. with stirring in a nitrogen atmosphere. Next, 1.52 g (0.0067 mol) of ammonium persulfate was added, and then a polymerization reaction was carried out at 50 ° C. for 4 hours. After the temperature was raised to 90 ° C., the polymerization reaction was carried out at 90 ° C. for 1 hour. The obtained aqueous solution was poured into methanol to precipitate a copolymer, which was recovered and vacuum dried to obtain a water-soluble acrylamide / acrylonitrile copolymer (AAm / AN copolymer).
このＡＡｍ／ＡＮ共重合体を重水に溶解し、得られた水溶液について、室温、周波数１００ＭＨｚの条件で１３Ｃ−ＮＭＲ測定を行なった。得られた１３Ｃ−ＮＭＲスペクトルにおいて、約１２１ｐｐｍ〜約１２２ｐｐｍに現れる、アクリロニトリルのシアノ基の炭素に由来するピークと約１７７ｐｐｍ〜約１８２ｐｐｍに現れる、アクリルアミドのカルボニル基の炭素に由来するピークとの強度比に基づいて、ＡＡｍ／ＡＮ共重合体中のアクリルアミド（ＡＡｍ）単位とアクリロニトリル（ＡＮ）単位との比を算出したところ、ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％であった。 This AAm / AN copolymer was dissolved in heavy water, and the resulting aqueous solution was subjected to 13 C-NMR measurement under conditions of room temperature and a frequency of 100 MHz. In the obtained 13 C-NMR spectrum, the intensity of the peak derived from carbon of the cyano group of acrylonitrile and the peak derived from carbon of the carbonyl group of acrylamide appearing from about 177 ppm to about 182 ppm appearing at about 121 ppm to about 122 ppm Based on the ratio, the ratio of acrylamide (AAm) units to acrylonitrile (AN) units in the AAm / AN copolymer was calculated, and it was AAm / AN = 75 mol% / 25 mol%.
（合成例４）
アクリルアミド（ＡＡｍ、和光純薬工業株式会社製）９６．０ｇ（１．３５ｍｏｌ）及びアクリロニトリル（ＡＮ）２３．９ｇ（０．４５ｍｏｌ）をイオン交換水４８０ｍｌに溶解し、得られた水溶液にテトラメチルエチレンジアミン６．７５ｍｌ（０．０４５ｍｏｌ）を添加して、窒素雰囲気下、撹拌しながら４０℃まで昇温した。次いで、過硫酸アンモニウム６．１７ｇ（０．０２７ｍｏｌ）を添加した後、６０℃で３時間重合反応を行なった。得られた水溶液をメタノール中に投入して共重合物を析出させ、これを回収して真空乾燥させることにより、水溶性のアクリルアミド／アクリロニトリル共重合体（ＡＡｍ／ＡＮ共重合体）を得た。このＡＡｍ／ＡＮ共重合体中のアクリルアミド（ＡＡｍ）単位とアクリロニトリル（ＡＮ）単位との比を合成例３と同様にして算出したところ、ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％であった。
(Synthesis Example 4)
Acrylamide (AAm, manufactured by Wako Pure Chemical Industries, Ltd.) 96.0 g (1.35 mol) and acrylonitrile (AN) 23.9 g (0.45 mol) were dissolved in 480 ml of ion-exchanged water, and tetramethylethylenediamine was added to the resulting aqueous solution. 6.75 ml (0.045 mol) was added and the temperature was raised to 40 ° C. with stirring in a nitrogen atmosphere. Next, 6.17 g (0.027 mol) of ammonium persulfate was added, and a polymerization reaction was performed at 60 ° C. for 3 hours. The obtained aqueous solution was poured into methanol to precipitate a copolymer, which was recovered and vacuum dried to obtain a water-soluble acrylamide / acrylonitrile copolymer (AAm / AN copolymer). When the ratio of acrylamide (AAm) units to acrylonitrile (AN) units in the AAm / AN copolymer was calculated in the same manner as in Synthesis Example 3, it was AAm / AN = 75 mol% / 25 mol%.
（合成例５）
アクリルアミド（ＡＡｍ、和光純薬工業株式会社製）９６．０ｇ（１．３５ｍｏｌ）及びアクリロニトリル（ＡＮ）２３．９ｇ（０．４５ｍｏｌ）をイオン交換水４８０ｍｌに溶解し、得られた水溶液にテトラメチルエチレンジアミン６．７５ｍｌ（０．０４５ｍｏｌ）を添加して、窒素雰囲気下、撹拌しながら６０℃まで昇温した。次いで、過硫酸アンモニウム２．５２ｇ（０．０１１ｍｏｌ）を添加した後、７８℃で３時間重合反応を行なった。得られた水溶液をメタノール中に投入して共重合物を析出させ、これを回収して真空乾燥させることにより、水溶性のアクリルアミド／アクリロニトリル共重合体（ＡＡｍ／ＡＮ共重合体）を得た。このＡＡｍ／ＡＮ共重合体中のアクリルアミド（ＡＡｍ）単位とアクリロニトリル（ＡＮ）単位との比を合成例３と同様にして算出したところ、ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％であった。
(Synthesis Example 5)
Acrylamide (AAm, manufactured by Wako Pure Chemical Industries, Ltd.) 96.0 g (1.35 mol) and acrylonitrile (AN) 23.9 g (0.45 mol) were dissolved in 480 ml of ion-exchanged water, and tetramethylethylenediamine was added to the resulting aqueous solution. 6.75 ml (0.045 mol) was added and the temperature was raised to 60 ° C. with stirring in a nitrogen atmosphere. Next, 2.52 g (0.011 mol) of ammonium persulfate was added, and a polymerization reaction was performed at 78 ° C. for 3 hours. The obtained aqueous solution was poured into methanol to precipitate a copolymer, which was recovered and vacuum dried to obtain a water-soluble acrylamide / acrylonitrile copolymer (AAm / AN copolymer). When the ratio of acrylamide (AAm) units to acrylonitrile (AN) units in the AAm / AN copolymer was calculated in the same manner as in Synthesis Example 3, it was AAm / AN = 75 mol% / 25 mol%.
（合成例６）
アクリルアミド（ＡＡｍ、和光純薬工業株式会社製）９６．０ｇ（１．３５ｍｏｌ）及びアクリロニトリル（ＡＮ）２３．９ｇ（０．４５ｍｏｌ）をイオン交換水１０８０ｍｌに溶解し、得られた水溶液に、窒素雰囲気下、室温で過硫酸アンモニウム６．１７ｇ（０．０２７ｍｏｌ）を添加した後、６０℃で３時間重合反応を行なった。得られた水溶液をメタノール中に投入して共重合物を析出させ、これを回収して真空乾燥させることにより、水溶性のアクリルアミド／アクリロニトリル共重合体（ＡＡｍ／ＡＮ共重合体）を得た。このＡＡｍ／ＡＮ共重合体中のアクリルアミド（ＡＡｍ）単位とアクリロニトリル（ＡＮ）単位との比を合成例３と同様にして算出したところ、ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％であった。
(Synthesis Example 6)
Acrylamide (AAm, manufactured by Wako Pure Chemical Industries, Ltd.) 96.0 g (1.35 mol) and acrylonitrile (AN) 23.9 g (0.45 mol) were dissolved in 1080 ml of ion-exchanged water, and a nitrogen atmosphere was added to the resulting aqueous solution. Then, 6.17 g (0.027 mol) of ammonium persulfate was added at room temperature, and a polymerization reaction was performed at 60 ° C. for 3 hours. The obtained aqueous solution was poured into methanol to precipitate a copolymer, which was recovered and vacuum dried to obtain a water-soluble acrylamide / acrylonitrile copolymer (AAm / AN copolymer). When the ratio of acrylamide (AAm) units to acrylonitrile (AN) units in the AAm / AN copolymer was calculated in the same manner as in Synthesis Example 3, it was AAm / AN = 75 mol% / 25 mol%.
（比較合成例１）
アクリルアミド（ＡＡｍ、和光純薬工業株式会社製）４８．０ｇ（０．６７５ｍｏｌ）及びアクリロニトリル（ＡＮ）１１．９５ｇ（０．２２５ｍｏｌ）をイオン交換水１１４０ｍｌに溶解し、得られた水溶液に、窒素雰囲気下、室温で過硫酸アンモニウム６．１７ｇ（０．０２７ｍｏｌ）を添加した後、６０℃で６時間重合反応を行なった。得られた水溶液をメタノール中に投入して共重合物を析出させ、これを回収して真空乾燥させることにより、水溶性のアクリルアミド／アクリロニトリル共重合体（ＡＡｍ／ＡＮ共重合体）を得た。このＡＡｍ／ＡＮ共重合体中のアクリルアミド（ＡＡｍ）単位とアクリロニトリル（ＡＮ）単位との比を合成例３と同様にして算出したところ、ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％であった。
(Comparative Synthesis Example 1)
Acrylamide (AAm, manufactured by Wako Pure Chemical Industries, Ltd.) 48.0 g (0.675 mol) and acrylonitrile (AN) 11.95 g (0.225 mol) were dissolved in 1140 ml of ion-exchanged water, and a nitrogen atmosphere was added to the resulting aqueous solution. Then, 6.17 g (0.027 mol) of ammonium persulfate was added at room temperature, and a polymerization reaction was performed at 60 ° C. for 6 hours. The obtained aqueous solution was poured into methanol to precipitate a copolymer, which was recovered and vacuum dried to obtain a water-soluble acrylamide / acrylonitrile copolymer (AAm / AN copolymer). When the ratio of acrylamide (AAm) units to acrylonitrile (AN) units in the AAm / AN copolymer was calculated in the same manner as in Synthesis Example 3, it was AAm / AN = 75 mol% / 25 mol%.
＜重量平均分子量Ｍｗ及び低分子量成分含有率の測定＞
合成例１〜２で得られたＰＡＡｍ並びに合成例３〜６及び比較合成例１で得られたＡＡｍ／ＡＮ共重合体の重量平均分子量Ｍｗ及び積分分子量分布を、ゲル浸透クロマトグラフィー（東ソー株式会社製「ＨＬＣ−８２２０ＧＰＣ」）を用いて下記の条件で測定した。
〔測定条件〕
カラム：ＴＳＫｇｅｌ ＧＭＰＷＸＬ×２本＋ＴＳＫｇｅｌ Ｇ２５００ＰＷＸＬ×１本。
溶離液：１００ｍＭ硝酸ナトリウム水溶液／アセトニトリル＝８０／２０。
溶離液流量：１．０ｍｌ／ｍｉｎ。
カラム温度：４０℃。
分子量標準物質：標準ポリエチレンオキシド／標準ポリエチレングリコール。
検出器：示差屈折率検出器。
<Measurement of weight average molecular weight Mw and low molecular weight component content>
The weight average molecular weight Mw and the integrated molecular weight distribution of the PAAm obtained in Synthesis Examples 1 and 2 and the AAm / AN copolymers obtained in Synthesis Examples 3 to 6 and Comparative Synthesis Example 1 were determined by gel permeation chromatography (Tosoh Corporation). Using “HLC-8220GPC”), measurement was performed under the following conditions.
〔Measurement condition〕
Column: TSKgel GMPW XL x 2 + TSKgel G2500PW XL x 1
Eluent: 100 mM aqueous sodium nitrate / acetonitrile = 80/20.
Eluent flow rate: 1.0 ml / min.
Column temperature: 40 ° C.
Molecular weight standard: standard polyethylene oxide / standard polyethylene glycol.
Detector: Differential refractive index detector.
表１に、重量平均分子量Ｍｗを示す。また、図１には、積分分子量分布曲線（横軸：分子量の対数値、縦軸：濃度分率の積分値）の一例として、合成例３で得られたＡＡｍ／ＡＮ共重合体の積分分子量分布曲線を示す。積分分子量分布曲線の縦軸は、ポリマー全体に対して、ある分子量以下の分子量を有する成分が占める割合を示していることから、各ＰＡＡｍ及びＡＡｍ／ＡＮ共重合体について、得られた積分分子量分布曲線に基づいて、ポリマー全体に対して分子量が５０００以下の低分子量成分の占める割合（低分子量成分含有率）を求めた。その結果を表１に示す。 Table 1 shows the weight average molecular weight Mw. FIG. 1 shows an integrated molecular weight distribution curve (horizontal axis: logarithmic value of molecular weight, vertical axis: integrated value of concentration fraction) as an example of the integrated molecular weight of the AAm / AN copolymer obtained in Synthesis Example 3. A distribution curve is shown. Since the vertical axis of the integral molecular weight distribution curve indicates the ratio of the component having a molecular weight below a certain molecular weight to the whole polymer, the integral molecular weight distribution obtained for each PAAm and AAm / AN copolymer Based on the curve, the ratio (low molecular weight component content) of the low molecular weight component having a molecular weight of 5000 or less to the whole polymer was determined. The results are shown in Table 1.
（実施例１）
炭素材料前駆体として合成例１で得られたＰＡＡｍ（Ｍｗ＝１３万、低分子量成分含有率＝２．５％）をそのまま使用した。
Example 1
The PAAm obtained in Synthesis Example 1 (Mw = 130,000, low molecular weight component content = 2.5%) was used as a carbon material precursor.
（実施例２）
炭素材料前駆体として合成例１で得られたＰＡＡｍ（Ｍｗ＝１３万、低分子量成分含有率＝２．５％）を、炭素材料前駆体濃度が２０質量％となるようにイオン交換水に溶解した。得られた水溶液に、前記炭素材料前駆体１００質量部に対して２質量部のリン酸水素二アンモニウムを添加し、撹拌して完全に溶解させた。得られた水溶液から水を減圧留去した後、得られた固体成分を真空乾燥して、ＰＡＡｍ及びリン酸水素二アンモニウムを含有する炭素材料前駆体組成物を得た。
(Example 2)
Dissolve PAAm (Mw = 130,000, low molecular weight component content = 2.5%) obtained in Synthesis Example 1 as a carbon material precursor in ion-exchanged water so that the carbon material precursor concentration is 20% by mass. did. To the obtained aqueous solution, 2 parts by mass of diammonium hydrogen phosphate was added with respect to 100 parts by mass of the carbon material precursor, and the mixture was stirred and completely dissolved. After distilling off water from the obtained aqueous solution under reduced pressure, the obtained solid component was vacuum-dried to obtain a carbon material precursor composition containing PAAm and diammonium hydrogen phosphate.
（実施例３）
炭素材料前駆体として合成例２で得られたＰＡＡｍ（Ｍｗ＝１３万、低分子量成分含有率＝１．５％）をそのまま使用した。
Example 3
The PAAm obtained in Synthesis Example 2 (Mw = 130,000, low molecular weight component content = 1.5%) was used as a carbon material precursor.
（実施例４）
炭素材料前駆体として合成例２で得られたＰＡＡｍ（Ｍｗ＝１３万、低分子量成分含有率＝１．５％）を用いた以外は実施例２と同様にして、ＰＡＡｍ及びリン酸水素二アンモニウムを含有する炭素材料前駆体組成物を得た。
Example 4
PAAm and diammonium hydrogen phosphate were obtained in the same manner as in Example 2 except that the PAAm obtained in Synthesis Example 2 (Mw = 130,000, low molecular weight component content = 1.5%) was used as the carbon material precursor. A carbon material precursor composition containing was obtained.
（実施例５）
リン酸水素二アンモニウムの代わりにリン酸を、前記炭素材料前駆体１００質量部に対して２質量部添加した以外は実施例４と同様にして、ＰＡＡｍ及びリン酸を含有する炭素材料前駆体組成物を得た。
(Example 5)
Carbon material precursor composition containing PAAm and phosphoric acid in the same manner as in Example 4 except that 2 parts by mass of phosphoric acid instead of diammonium hydrogen phosphate was added to 100 parts by mass of the carbon material precursor. I got a thing.
（実施例６）
炭素材料前駆体として合成例３で得られたＡＡｍ／ＡＮ共重合体（ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％、Ｍｗ＝１３万、低分子量成分含有率＝１．５％）をそのまま使用した。
(Example 6)
The AAm / AN copolymer (AAm / AN = 75 mol% / 25 mol%, Mw = 130,000, low molecular weight component content = 1.5%) obtained in Synthesis Example 3 was used as a carbon material precursor.
（実施例７）
炭素材料前駆体として合成例３で得られたＡＡｍ／ＡＮ共重合体（ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％、Ｍｗ＝１３万、低分子量成分含有率＝１．５％）を用いた以外は実施例２と同様にして、ＡＡｍ／ＡＮ共重合体及びリン酸水素二アンモニウムを含有する炭素材料前駆体組成物を得た。
(Example 7)
AAm / AN copolymer obtained in Synthesis Example 3 (AAm / AN = 75 mol% / 25 mol%, Mw = 130,000, low molecular weight component content = 1.5%) was used as the carbon material precursor. In the same manner as in Example 2, a carbon material precursor composition containing an AAm / AN copolymer and diammonium hydrogen phosphate was obtained.
（実施例８）
炭素材料前駆体として合成例４で得られたＡＡｍ／ＡＮ共重合体（ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％、Ｍｗ＝５．４万、低分子量成分含有率＝５．０％）をそのまま使用した。
(Example 8)
AAm / AN copolymer (AAm / AN = 75 mol% / 25 mol%, Mw = 54,000, low molecular weight component content = 5.0%) obtained in Synthesis Example 4 is used as the carbon material precursor. did.
（実施例９）
炭素材料前駆体として合成例４で得られたＡＡｍ／ＡＮ共重合体（ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％、Ｍｗ＝５．４万、低分子量成分含有率＝５．０％）を用い、リン酸水素二アンモニウムの添加量を前記炭素材料前駆体１００質量部に対して５質量部に変更した以外は実施例２と同様にして、ＡＡｍ／ＡＮ共重合体及びリン酸水素二アンモニウムを含有する炭素材料前駆体組成物を得た。
Example 9
Using the AAm / AN copolymer (AAm / AN = 75 mol% / 25 mol%, Mw = 54,000, low molecular weight component content = 5.0%) obtained in Synthesis Example 4 as the carbon material precursor, Contains AAm / AN copolymer and diammonium hydrogen phosphate in the same manner as in Example 2 except that the addition amount of diammonium hydrogen phosphate is changed to 5 parts by mass with respect to 100 parts by mass of the carbon material precursor. A carbon material precursor composition was obtained.
（実施例１０）
炭素材料前駆体として合成例５で得られたＡＡｍ／ＡＮ共重合体（ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％、Ｍｗ＝５．４万、低分子量成分含有率＝２．０％）をそのまま使用した。
(Example 10)
The AAm / AN copolymer obtained in Synthesis Example 5 (AAm / AN = 75 mol% / 25 mol%, Mw = 54,000, low molecular weight component content = 2.0%) is used as it is as a carbon material precursor. did.
（実施例１１）
炭素材料前駆体として合成例５で得られたＡＡｍ／ＡＮ共重合体（ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％、Ｍｗ＝５．４万、低分子量成分含有率＝２．０％）を用いた以外は実施例２と同様にして、ＡＡｍ／ＡＮ共重合体及びリン酸水素二アンモニウムを含有する炭素材料前駆体組成物を得た。
(Example 11)
The AAm / AN copolymer obtained in Synthesis Example 5 (AAm / AN = 75 mol% / 25 mol%, Mw = 54,000, low molecular weight component content = 2.0%) was used as the carbon material precursor. Except for the above, a carbon material precursor composition containing an AAm / AN copolymer and diammonium hydrogen phosphate was obtained in the same manner as in Example 2.
（実施例１２）
リン酸水素二アンモニウムの添加量を前記炭素材料前駆体１００質量部に対して５質量部に変更した以外は実施例１１と同様にして、ＡＡｍ／ＡＮ共重合体及びリン酸水素二アンモニウムを含有する炭素材料前駆体組成物を得た。
(Example 12)
AAm / AN copolymer and diammonium hydrogen phosphate are contained in the same manner as in Example 11 except that the addition amount of diammonium hydrogen phosphate is changed to 5 parts by mass with respect to 100 parts by mass of the carbon material precursor. A carbon material precursor composition was obtained.
（実施例１３）
リン酸水素二アンモニウムの代わりにホウ酸を、前記炭素材料前駆体１００質量部に対して２質量部添加した以外は実施例１１と同様にして、ＰＡＡｍ及びリン酸を含有する炭素材料前駆体組成物を得た。
(Example 13)
Carbon material precursor composition containing PAAm and phosphoric acid in the same manner as in Example 11 except that boric acid was added in place of 100 parts by mass of the carbon material precursor instead of diammonium hydrogen phosphate. I got a thing.
（実施例１４）
炭素材料前駆体として合成例６で得られたＡＡｍ／ＡＮ共重合体（ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％、Ｍｗ＝４５万、低分子量成分含有率＝６．０％）をそのまま使用した。
(Example 14)
The AAm / AN copolymer obtained in Synthesis Example 6 (AAm / AN = 75 mol% / 25 mol%, Mw = 450,000, low molecular weight component content = 6.0%) was used as it was as the carbon material precursor.
（比較例１）
炭素材料前駆体として比較合成例１で得られたＡＡｍ／ＡＮ共重合体（ＡＡｍ／ＡＮ＝７５ｍｏｌ％／２５ｍｏｌ％、Ｍｗ＝５．７万、低分子量成分含有率＝８．０％）をそのまま使用した。
(Comparative Example 1)
The AAm / AN copolymer (AAm / AN = 75 mol% / 25 mol%, Mw = 57,000, low molecular weight component content = 8.0%) obtained in Comparative Synthesis Example 1 as a carbon material precursor is used as it is. used.
（比較例２）
炭素材料前駆体としてポリアクリロニトリル（ＰＡＮ、シグマ−アルドリッチ社製、製品番号：１８１３１５、重量平均分子量：１５万）をそのまま使用した。
(Comparative Example 2)
As the carbon material precursor, polyacrylonitrile (PAN, manufactured by Sigma-Aldrich, product number: 181315, weight average molecular weight: 150,000) was used as it was.
＜耐炎化収率の測定＞
実施例及び比較例で得られた炭素材料前駆体（実施例１、３、６、８、１０、１４、比較例１、２）又は炭素材料前駆体組成物（実施例２、４〜５、７、９、１１〜１３）を８０℃で１２時間真空乾燥した後、３ｍｇ秤量し、示差熱天秤（株式会社リガク製「ＴＧ８１２０」）を用いて、空気流量５００ｍｌ／ｍｉｎの空気雰囲気下、昇温速度１０℃／ｍｉｎで室温から３００℃まで加熱し、３００℃で１０分間保持（耐炎化処理）して炭素材料前駆体又は炭素材料前駆体組成物の耐炎化物を得た。耐炎化処理前後の炭素材料前駆体の質量保持率（炭素材料前駆体の耐炎化収率）を、前記真空乾燥後に炭素材料前駆体に吸着した水の影響を考慮し、１５０℃における炭素材料前駆体の質量を基準として、下記式：
炭素材料前駆体の耐炎化収率［％］＝Ｍ３００／Ｍ１５０×１００
〔Ｍ３００：空気雰囲気下、３００℃で１０分間加熱した後の炭素材料前駆体（耐炎化物）の質量、Ｍ１５０：１５０℃における炭素材料前駆体の質量〕
により求めた。その結果を表２に示す。
<Measurement of flameproofing yield>
Carbon material precursors obtained in Examples and Comparative Examples (Examples 1, 3, 6, 8, 10, 14, Comparative Examples 1 and 2) or carbon material precursor compositions (Examples 2, 4 to 5, 7, 9, 11-13) are vacuum-dried at 80 ° C. for 12 hours, and then 3 mg is weighed. It heated from room temperature to 300 degreeC with the temperature rate of 10 degreeC / min, and hold | maintained at 300 degreeC for 10 minutes (flameproofing treatment), and obtained the flameproofed material of the carbon material precursor or the carbon material precursor composition. Considering the influence of water adsorbed on the carbon material precursor after the vacuum drying, the mass retention rate of the carbon material precursor before and after the flameproofing treatment (the flameproofing yield of the carbon material precursor) Based on body mass, the following formula:
Flame resistant yield of carbon material precursor [%] = M 300 / M 150 × 100
[M 300 : mass of carbon material precursor (flame-resistant product) after heating at 300 ° C. for 10 minutes under air atmosphere, M 150 : mass of carbon material precursor at 150 ° C.]
Determined by The results are shown in Table 2.
＜炭化収率の測定＞
前記炭素材料前駆体の耐炎化物（実施例１、３、６、８、１０、１４、比較例１、２）又は前記炭素材料前駆体組成物の耐炎化物（実施例２、４〜５、７、９、１１〜１３）２ｍｇを示差熱天秤（株式会社リガク製「ＴＧ８１２０」）を用いて、窒素流量５００ｍｌ／ｍｉｎの窒素雰囲気下、昇温速度２０℃／ｍｉｎで室温から１１００℃まで加熱（炭化処理）して炭素材料を得た。この炭化処理前後の耐炎化物の質量保持率（１１００℃における耐炎化物の炭化収率）を、耐炎化物に吸着した水の影響を考慮し、１５０℃における耐炎化物の質量を基準として、下記式：
耐炎化物の炭化収率［％］＝Ｍ１１００／Ｍ１５０×１００
〔Ｍ１１００：窒素雰囲気下、１１００℃まで加熱した後の耐炎化物（炭素材料）の質量、Ｍ１５０：１５０℃における耐炎化物の質量〕
により求めた。その結果を表２に示す。
<Measurement of carbonization yield>
Flame-resistant products of the carbon material precursor (Examples 1, 3, 6, 8, 10, 14, Comparative Examples 1 and 2) or flame-retardant products of the carbon material precursor composition (Examples 2, 4 to 5, 7) , 9, 11-13) 2 mg was heated from room temperature to 1100 ° C. at a heating rate of 20 ° C./min in a nitrogen atmosphere with a nitrogen flow rate of 500 ml / min using a differential thermobalance (“TG8120” manufactured by Rigaku Corporation) ( Carbonized to obtain a carbon material. Considering the influence of water adsorbed on the flameproofing material, the mass retention rate of the flameproofing material before and after the carbonization treatment (carbonization yield of the flameproofing material at 1100 ° C.) is based on the following formula:
Carbonization yield [%] of flame retardant: M 1100 / M 150 × 100
[M 1100 : Mass of flame-resistant product (carbon material) after heating to 1100 ° C. under nitrogen atmosphere, M 150 : Mass of flame-resistant product at 150 ° C.]
Determined by The results are shown in Table 2.
＜耐炎化・炭化の総収率の算出＞
実施例及び比較例で得られた炭素材料前駆体又は炭素材料前駆体組成物の耐炎化・炭化の総収率を、下記式：
耐炎化・炭化の総収率［％］＝（耐炎化収率／１００）×（炭化収率／１００）×１００
により求めた。その結果を表２に示す。
<Calculation of total yield of flame resistance and carbonization>
The total yield of the flame resistance and carbonization of the carbon material precursors or carbon material precursor compositions obtained in the examples and comparative examples is expressed by the following formula:
Total yield of flameproofing / carbonization [%] = (flameproofing yield / 100) × (carbonization yield / 100) × 100
Determined by The results are shown in Table 2.
表２に示したように、所定の重量平均分子量を有し、かつ、所定の低分子量成分含有率を有するアクリルアミド系ポリマーからなる本発明の炭素材料前駆体（実施例１、３、６、８、１０、１４）及びそれを含有する本発明の炭素材料前駆体組成物（実施例２、４〜５、７、９、１１〜１３）は、従来のポリアクリロニトリルからなる炭素材料前駆体（比較例２）に比べて、耐炎化物の炭化収率及び耐炎化と炭化の総収率が高くなることが確認された。 As shown in Table 2, the carbon material precursor of the present invention (Examples 1, 3, 6, 8) comprising an acrylamide polymer having a predetermined weight average molecular weight and a predetermined low molecular weight component content. 10, 14) and the carbon material precursor composition of the present invention containing the same (Examples 2, 4-5, 7, 9, 11-13) are carbon material precursors made of conventional polyacrylonitrile (comparison). Compared to Example 2), it was confirmed that the carbonization yield of the flameproofed product and the total yield of flameproofing and carbonization were increased.
また、所定の重量平均分子量を有し、かつ、所定の低分子量成分含有率を有するアクリルアミド系ポリマーからなる本発明の炭素材料前駆体（実施例８、１０）は、同等の重量平均分子量を有し、低分子量成分含有率が所定の範囲を超えるアクリルアミド系ポリマーからなる炭素材料前駆体（比較例１）に比べて、耐炎化収率、耐炎化物の炭化収率、及び耐炎化と炭化の総収率が高くなることが確認された。 In addition, the carbon material precursors of the present invention (Examples 8 and 10) made of an acrylamide polymer having a predetermined weight average molecular weight and a predetermined low molecular weight component content have equivalent weight average molecular weights. Compared with the carbon material precursor (Comparative Example 1) composed of an acrylamide polymer whose low molecular weight component content exceeds a predetermined range, the flameproofing yield, the carbonized yield of the flameproofed product, and the total flameproofing and carbonization It was confirmed that the yield was high.
さらに、実施例６と実施例３とを対比すると明らかなように、所定の重量平均分子量を有し、かつ、所定の低分子量成分含有率を有するアクリルアミド／アクリロニトリル共重合体からなる炭素材料前駆体（実施例６）は、同等の重量平均分子量及び同等の低分子量成分含有率を有するアクリルアミドの単独重合体からなる炭素材料前駆体（実施例３）に比べて、耐炎化物の炭化収率及び耐炎化と炭化の総収率が高くなることがわかった。 Further, as apparent from comparison between Example 6 and Example 3, a carbon material precursor comprising an acrylamide / acrylonitrile copolymer having a predetermined weight average molecular weight and a predetermined low molecular weight component content. (Example 6) shows a carbonization yield and flame resistance of the flame-resistant product as compared with a carbon material precursor (Example 3) made of a homopolymer of acrylamide having an equivalent weight average molecular weight and an equivalent low molecular weight component content. It was found that the total yield of crystallization and carbonization was high.
また、実施例１と実施例３、実施例２と実施例４〜５、実施例８と実施例１０、実施例９と実施例１１〜１３とを対比すると明らかなように、同等の重量平均分子量を有し、同種のアクリルアミド系ポリマーからなる炭素材料前駆体及びそれを含有する炭素材料前駆体組成物においては、低分子量成分含有率が小さくなると、耐炎化収率、耐炎化物の炭化収率、及び耐炎化と炭化の総収率が増加することがわかった。 Further, as is clear when Example 1 and Example 3, Example 2 and Examples 4 to 5, Example 8 and Example 10, Example 9 and Examples 11 to 13 are compared, equivalent weight averages In a carbon material precursor having a molecular weight and the same kind of acrylamide polymer and a carbon material precursor composition containing the same, if the low molecular weight component content decreases, the flameproofing yield and the carbonized yield of the flameproofed product And the overall yield of flame resistance and carbonization was found to increase.
さらに、実施例２と実施例１、実施例４〜５と実施例３、実施例７と実施例６、実施例９と実施例８、実施例１１〜１３と実施例１０とを対比すると明らかなように、所定の重量平均分子量を有し、かつ、所定の低分子量成分含有率を有するアクリルアミド系ポリマーからなる炭素材料前駆体に所定量のリン酸、ホウ酸、又はリン酸塩を添加した炭素材料前駆体組成物（実施例２、４〜５、７、９、１１〜１３）は、リン酸及びリン酸塩を添加しなかった場合（実施例１、３、６、８、１０）に比べて、耐炎化物の炭化収率及び耐炎化と炭化の総収率が増加することがわかった。 Further, it is clear that Example 2 and Example 1, Examples 4 to 5 and Example 3, Example 7 and Example 6, Example 9 and Example 8, Example 11 to 13 and Example 10 are compared. As described above, a predetermined amount of phosphoric acid, boric acid, or phosphate was added to a carbon material precursor composed of an acrylamide polymer having a predetermined weight average molecular weight and a predetermined low molecular weight component content. The carbon material precursor composition (Examples 2, 4 to 5, 7, 9, 11 to 13) was not added with phosphoric acid and phosphate (Examples 1, 3, 6, 8, and 10). It was found that the carbonization yield of the flame retardant and the total yield of flame resistance and carbonization increased.
また、実施例１２と実施例１１とを対比すると明らかなように、添加成分の量が増加すると、耐炎化収率、耐炎化物の炭化収率、及び耐炎化と炭化の総収率が増加することがわかった。 Further, as apparent from the comparison between Example 12 and Example 11, when the amount of the additive component increases, the flameproofing yield, the carbonized yield of the flameproofed product, and the total yield of flameproofing and carbonizing increase. I understood it.
〔耐炎化処理温度の影響〕
＜耐炎化収率の測定＞
実施例６で得られた炭素材料前駆体、実施例９、１２で得られた炭素材料前駆体組成物、比較例１、２で得られた炭素材料前駆体を８０℃で１２時間真空乾燥した後、３ｍｇ秤量し、示差熱天秤（株式会社リガク製「ＴＧ８１２０」）を用いて、空気流量５００ｍｌ／ｍｉｎの空気雰囲気下、昇温速度１０℃／ｍｉｎで室温から所定温度まで加熱し、所定温度で所定時間保持（耐炎化処理）して炭素材料前駆体又は炭素材料前駆体組成物の耐炎化物を得た。耐炎化処理前後の炭素材料前駆体の質量保持率（炭素材料前駆体の耐炎化収率）を、前記真空乾燥後に炭素材料前駆体に吸着した水の影響を考慮し、１５０℃における炭素材料前駆体の質量を基準として、下記式：
炭素材料前駆体の耐炎化収率［％］＝ＭＴ／Ｍ１５０×１００
〔ＭＴ：空気雰囲気下、所定温度Ｔ［℃］で所定時間加熱した後の炭素材料前駆体（耐炎化物）の質量、Ｍ１５０：１５０℃における炭素材料前駆体の質量〕
により求めた。その結果を表３に示す。
[Effect of flameproofing temperature]
<Measurement of flameproofing yield>
The carbon material precursor obtained in Example 6, the carbon material precursor composition obtained in Examples 9 and 12, and the carbon material precursor obtained in Comparative Examples 1 and 2 were vacuum-dried at 80 ° C. for 12 hours. Thereafter, 3 mg was weighed and heated from room temperature to a predetermined temperature at a heating rate of 10 ° C./min in an air atmosphere with an air flow rate of 500 ml / min using a differential thermal balance (“TG8120” manufactured by Rigaku Corporation). Was held for a predetermined time (flame-proofing treatment) to obtain a flame-proof material of the carbon material precursor or the carbon material precursor composition. Considering the influence of water adsorbed on the carbon material precursor after the vacuum drying, the mass retention rate of the carbon material precursor before and after the flameproofing treatment (the flameproofing yield of the carbon material precursor) Based on body mass, the following formula:
Flameproof yield of carbon material precursor [%] = M T / M 150 × 100
[M T : mass of carbon material precursor (flame-resistant product) after heating for a predetermined time at a predetermined temperature T [° C.] in air atmosphere, M 150 : mass of carbon material precursor at 150 ° C.]
Determined by The results are shown in Table 3.
＜炭化収率の測定＞
前記炭素材料前駆体の耐炎化物（実施例６、比較例１、２）、前記炭素材料前駆体組成物の耐炎化物（実施例９、１２）、耐炎化処理を施していない前記炭素材料前駆体組成物（実施例１２）又は耐炎化処理を施していない前記炭素材料前駆体（比較例２）２ｍｇを示差熱天秤（株式会社リガク製「ＴＧ８１２０」）を用いて、窒素流量５００ｍｌ／ｍｉｎの窒素雰囲気下、昇温速度２０℃／ｍｉｎで室温から１１００℃まで加熱（炭化処理）して炭素材料を得た。この炭化処理前後の耐炎化物の質量保持率（１１００℃における耐炎化物の炭化収率）を、耐炎化物に吸着した水の影響を考慮し、１５０℃における耐炎化物の質量を基準として、下記式：
耐炎化物の炭化収率［％］＝Ｍ１１００／Ｍ１５０×１００
〔Ｍ１１００：窒素雰囲気下、１１００℃まで加熱した後の耐炎化物（炭素材料）の質量、Ｍ１５０：１５０℃における耐炎化物の質量〕
により求めた。その結果を表３に示す。なお、耐炎化処理を施していない炭素材料前駆体の耐炎化収率は１００％とした。
<Measurement of carbonization yield>
Flame-resistant product of the carbon material precursor (Example 6, Comparative Examples 1 and 2), Flame-resistant product of the carbon material precursor composition (Examples 9 and 12), and the carbon material precursor not subjected to flameproofing treatment Using a differential thermal balance (“TG8120” manufactured by Rigaku Corporation) 2 mg of the composition (Example 12) or the carbon material precursor (Comparative Example 2) not subjected to flameproofing treatment, nitrogen having a nitrogen flow rate of 500 ml / min. Under an atmosphere, a carbon material was obtained by heating (carbonization treatment) from room temperature to 1100 ° C. at a temperature rising rate of 20 ° C./min. Considering the influence of water adsorbed on the flameproofing material, the mass retention rate of the flameproofing material before and after the carbonization treatment (carbonization yield of the flameproofing material at 1100 ° C.) is based on the following formula:
Carbonization yield [%] of flame retardant: M 1100 / M 150 × 100
[M 1100 : Mass of flame-resistant product (carbon material) after heating to 1100 ° C. under nitrogen atmosphere, M 150 : Mass of flame-resistant product at 150 ° C.]
Determined by The results are shown in Table 3. In addition, the flameproofing yield of the carbon material precursor not subjected to the flameproofing treatment was 100%.
＜耐炎化・炭化の総収率の算出＞
実施例６で得られた炭素材料前駆体、実施例９、１２で得られた炭素材料前駆体組成物、比較例１、２で得られた炭素材料前駆体の耐炎化・炭化の総収率を、下記式：
耐炎化・炭化の総収率［％］＝（耐炎化収率／１００）×（炭化収率／１００）×１００
により求めた。その結果を表３に示す。
<Calculation of total yield of flame resistance and carbonization>
Total yield of flame resistance and carbonization of the carbon material precursor obtained in Example 6, the carbon material precursor composition obtained in Examples 9 and 12, and the carbon material precursor obtained in Comparative Examples 1 and 2 The following formula:
Total yield of flameproofing / carbonization [%] = (flameproofing yield / 100) × (carbonization yield / 100) × 100
Determined by The results are shown in Table 3.
表３に示したように、耐炎化処理温度が低くなるにつれて、炭素材料前駆体の耐炎化収率は高くなるものの、耐炎化と炭化の総収率（最終的に得られる炭素材料の収率）が高くなるという観点においては、好適な耐炎化処理温度範囲が存在することがわかった。 As shown in Table 3, although the flameproofing yield of the carbon material precursor increases as the flameproofing temperature decreases, the total yield of flameproofing and carbonization (the yield of the carbon material finally obtained) ) Is high, it has been found that there is a suitable flameproofing temperature range.
また、耐炎化処理温度を３５０℃に変更した場合でも、耐炎化処理温度が３００℃の場合と同様に、所定の重量平均分子量を有し、かつ、所定の低分子量成分含有率を有するアクリルアミド系ポリマーからなる本発明の炭素材料前駆体（実施例６）及びそれを含有する本発明の炭素材料前駆体組成物（実施例９、１２）は、低分子量成分含有率が所定の範囲を超えるアクリルアミド系ポリマーからなる炭素材料前駆体（比較例１）に比べて、耐炎化収率、耐炎化物の炭化収率、及び耐炎化と炭化の総収率が高くなり、また、従来のポリアクリロニトリルからなる炭素材料前駆体（比較例２）に比べて、耐炎化物の炭化収率及び耐炎化と炭化の総収率が高くなることがわかった。 Further, even when the flameproofing treatment temperature is changed to 350 ° C., the acrylamide type having a predetermined weight average molecular weight and a predetermined low molecular weight component content, as in the case where the flameproofing processing temperature is 300 ° C. The carbon material precursor of the present invention comprising a polymer (Example 6) and the carbon material precursor composition of the present invention (Examples 9 and 12) containing the polymer are acrylamide whose low molecular weight component content exceeds a predetermined range. Compared with a carbon material precursor (Comparative Example 1) made of a polymer, the flameproofing yield, the carbonized yield of the flameproofed product, and the total yield of flameproofing and carbonization are increased, and it is made of conventional polyacrylonitrile. Compared to the carbon material precursor (Comparative Example 2), it was found that the carbonization yield of the flame-resistant product and the total yield of flame resistance and carbonization were increased.
さらに、実施例９と実施例１２とを対比すると明らかなように、同等の重量平均分子量を有し、同種のアクリルアミド系ポリマーからなる炭素材料前駆体を含有する炭素材料前駆体組成物においては、耐炎化と炭化の総収率が、耐炎化処理条件によらず、低分子量成分含有率が小さいものの方が高くなることがわかった。 Further, as is clear from comparison between Example 9 and Example 12, in the carbon material precursor composition containing the carbon material precursor having the same weight average molecular weight and composed of the same kind of acrylamide polymer, It has been found that the total yield of flame resistance and carbonization is higher when the low molecular weight component content is smaller, regardless of the flame resistance treatment conditions.
また、実施例１２と比較例１、２とを対比すると明らかなように、所定の重量平均分子量を有し、かつ、所定の低分子量成分含有率を有するアクリルアミド系ポリマーからなる炭素材料前駆体を含有する本発明の炭素材料前駆体組成物（実施例１２）は、耐炎化処理を施さなくても、最終的に得られる炭素材料の収率（炭化収率）が、従来のポリアクリロニトリルからなる炭素材料前駆体（比較例２）に耐炎化処理を施さなかった場合に最終的に得られる炭素材料の収率（炭化収率）に比べて高くなり、さらに、低分子量成分含有率が所定の範囲を超えるアクリルアミド系ポリマーからなる炭素材料前駆体（比較例１）又は従来のポリアクリロニトリルからなる炭素材料前駆体（比較例２）に耐炎化処理と炭化処理とを施した場合に最終的に得られる炭素材料の収率（耐炎化と炭化の総収率）に比べても高くなることがわかった。 Further, as is clear from comparison between Example 12 and Comparative Examples 1 and 2, a carbon material precursor comprising an acrylamide polymer having a predetermined weight average molecular weight and a predetermined low molecular weight component content is obtained. Even if the carbon material precursor composition (Example 12) of the present invention contained is not subjected to flameproofing treatment, the yield of carbon material finally obtained (carbonization yield) is made of conventional polyacrylonitrile. If the carbon material precursor (Comparative Example 2) is not subjected to a flameproofing treatment, the carbon material is finally obtained in a higher yield (carbonization yield), and the low molecular weight component content is predetermined. When a carbon material precursor (Comparative Example 1) made of an acrylamide polymer exceeding the range or a carbon material precursor made of a conventional polyacrylonitrile (Comparative Example 2) is subjected to flameproofing treatment and carbonization treatment, finally It was found to be higher than the yield (total yield of oxidization and carbonization) of the carbon material to be.
以上説明したように、本発明によれば、アクリルアミド系ポリマーからなり、高収率で炭素材料を得ることが可能な炭素材料前駆体及びそれを含有する炭素材料前駆体組成物を得ることができる。 As described above, according to the present invention, a carbon material precursor made of an acrylamide polymer and capable of obtaining a carbon material in a high yield and a carbon material precursor composition containing the carbon material precursor can be obtained. .
したがって、本発明の炭素材料の製造方法は、使用する炭素材料前駆体が炭素材料の収率が高いものであるため、低コストで効率よく安定して炭素材料を製造することが可能な方法として有用である。 Therefore, since the carbon material precursor to be used has a high carbon material yield, the carbon material production method of the present invention is a method capable of producing a carbon material efficiently and stably at low cost. Useful.
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