JP2011037766A - 5(6)-amino-2-(4-aminophenyl)benzimidazole and adjusting method thereof - Google Patents
5(6)-amino-2-(4-aminophenyl)benzimidazole and adjusting method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 5
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000002076 thermal analysis method Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 18
- 229920000642 polymer Polymers 0.000 abstract description 15
- 238000009987 spinning Methods 0.000 abstract description 10
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- PQOPJKRIAWTTJQ-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole-4,5-diamine Chemical compound N=1C2=C(N)C(N)=CC=C2NC=1C1=CC=CC=C1 PQOPJKRIAWTTJQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 14
- 238000005259 measurement Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 150000004985 diamines Chemical class 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 polyparaphenylene terephthalamide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VQFBXSRZSUJGOF-UHFFFAOYSA-N 4-(1h-benzimidazol-2-yl)aniline Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=CC=C2N1 VQFBXSRZSUJGOF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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Abstract
Description
本発明は、５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾールおよびその調整方法に関する。さらに詳しくは、芳香族ポリアミドの重合に適した５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾールに関する。 The present invention relates to 5 (6) -amino-2- (4-aminophenyl) benzimidazole and a preparation method thereof. More specifically, it relates to 5 (6) -amino-2- (4-aminophenyl) benzimidazole suitable for the polymerization of aromatic polyamide.
従来、芳香族ジカルボン酸成分と芳香族ジアミン成分とからなるアラミド繊維、特にポリパラフェニレンテレフタルアミド（ＰＰＴＡ）繊維等のパラ系のアラミド繊維は、その強度、高弾性率、高耐熱性といった特性を活かして、産業用途、衣料用途等に広く用いられている。しかしながら、繊維強度、弾性率等の機械的物性は、用いられる用途によっては未だ十分に満足できるものではなく、機械的物性の向上を目指してさらなる開発がすすめられており、分子鎖に剛直な構造を有し、かつ、分子間相互作用の強いモノマー分子の導入により、繊維の機械的物性の向上が期待できることが知られている。 Conventionally, aramid fibers composed of an aromatic dicarboxylic acid component and an aromatic diamine component, particularly para-aramid fibers such as polyparaphenylene terephthalamide (PPTA) fibers, have characteristics such as strength, high elastic modulus, and high heat resistance. Utilizing it, it is widely used for industrial use, clothing use and so on. However, the mechanical properties such as fiber strength and elastic modulus are still not fully satisfactory depending on the application used, and further development has been promoted with the aim of improving the mechanical properties. It is known that the mechanical properties of the fiber can be expected to be improved by introducing a monomer molecule having a strong intermolecular interaction.
このような目的を満たす化合物の一つとして、式（１）で表されるジアミン、５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール（以下ＤＡＰＢＩと呼ぶこともある）が挙げられる。そして、本化合物は、例えば特許文献１および２に記載された方法により得ることができ、また、試薬としても販売されている（ＣＡＳ Ｎｏ．７６２１−８６−５、ＡＫ Ｓｃｉｅｎｔｉｆｉｃ Ｉｎｃ．）。 One example of a compound that satisfies such a purpose is a diamine represented by the formula (1), 5 (6) -amino-2- (4-aminophenyl) benzimidazole (hereinafter sometimes referred to as DAPBI). . The present compound can be obtained, for example, by the methods described in Patent Documents 1 and 2, and is also sold as a reagent (CAS No. 7621-86-5, AK Scientific Inc.).
しかしながら、合成されたＤＡＰＢＩを調整することなく重合を行った場合には、ゲル化や高粘度化によるポリマー溶液の流動性低下が起こり、紡糸に適したポリマー溶液を得ることが困難であった。 However, when the polymerization was performed without adjusting the synthesized DAPBI, the fluidity of the polymer solution was lowered due to gelation or increased viscosity, and it was difficult to obtain a polymer solution suitable for spinning.
したがって、重合溶液の粘度（重合度）を制御でき、かつ、得られるポリマーの未溶解物が抑制された均一なポリマー溶液を得るのに適した式（１）で表されるジアミン（ＤＡＰＢＩ）については、未だ提案されていないのが実情であった。 Therefore, the diamine (DAPBI) represented by the formula (1) suitable for obtaining a uniform polymer solution in which the viscosity (polymerization degree) of the polymerization solution can be controlled and the undissolved polymer obtained is suppressed. The actual situation has not yet been proposed.
本発明は、かかる従来技術を背景になされたもので、その目的は、ポリアミド重合時におけるゲル化、高粘度化による流動性の低下を抑制し、紡糸に適した重合度に制御可能で、得られたポリマーの未溶解物が抑制された均一なポリマー溶液を得ることのできるＤＡＰＢＩを提供することにある。 The present invention has been made against the background of such conventional technology, and its purpose is to suppress the decrease in fluidity due to gelation and viscosity increase during polyamide polymerization, and to control the degree of polymerization suitable for spinning. An object of the present invention is to provide a DAPBI capable of obtaining a uniform polymer solution in which undissolved polymer is suppressed.
本発明者は、上記課題を解決するため鋭意検討した。その結果、ＤＡＰＢＩを特定の温度範囲で乾燥させることにより、熱分析における吸熱ピークの比率が特定の範囲に制御され、かつ、水分率が低下したＤＡＰＢＩを得ることができ、当該ＤＡＰＢＩによれば、上記の課題を解決できることを見出し、本発明を完成するに至った。 The present inventor has intensively studied to solve the above problems. As a result, by drying DAPBI in a specific temperature range, the ratio of endothermic peaks in thermal analysis can be controlled to a specific range, and DAPBI with a reduced moisture content can be obtained. According to the DAPBI, The present inventors have found that the above problems can be solved and have completed the present invention.
すなわち本発明は、熱分析において、２１０℃〜２３０℃の範囲に観測される第１の吸熱ピーク、および、２３５℃〜２５０℃の範囲に観測される第２の吸熱ピークを有し、かつ、第２の吸熱ピークに対する第１の吸熱ピークの比が０．８以上であり、
水分率が１００ｐｐｍ以下である５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール（式（１））である。
That is, the present invention has a first endothermic peak observed in the range of 210 ° C. to 230 ° C. and a second endothermic peak observed in the range of 235 ° C. to 250 ° C. in thermal analysis, and The ratio of the first endothermic peak to the second endothermic peak is 0.8 or more;
5 (6) -amino-2- (4-aminophenyl) benzimidazole (formula (1)) having a moisture content of 100 ppm or less.
また別の本発明は、１２０℃以上１８０℃以下の温度範囲で、窒素雰囲気下において大気圧下３０分以上熱乾燥処理を行う請求項１記載の５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾールの調整方法である。 In another aspect of the present invention, 5 (6) -amino-2- (4-) according to claim 1, wherein the heat drying treatment is performed in a temperature range of 120 ° C. or higher and 180 ° C. or lower in a nitrogen atmosphere at atmospheric pressure for 30 minutes or longer. Aminophenyl) benzimidazole preparation method.
本発明のＤＡＰＢＩによれば、ポリアミド重合時におけるゲル化、高粘度化による流動性の低下を抑制し、得られたポリマーの未溶解物が抑制された均一なポリマー溶液を得ることのできる。このため、紡糸に適した重合度に制御された芳香族コポリアミド溶液を、安定的に効率よく得ることができる。 According to DAPBI of the present invention, it is possible to suppress a decrease in fluidity due to gelation and increase in viscosity during polyamide polymerization, and to obtain a uniform polymer solution in which undissolved polymer obtained is suppressed. For this reason, the aromatic copolyamide solution controlled to the degree of polymerization suitable for spinning can be stably and efficiently obtained.
以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
＜５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール（ＤＡＰＢＩ）（ＤＡＰＢＩ）＞
本発明で用いるＤＡＰＢＩ（式（１））は、従来公知の方法にしたがって製造する事ができる。また、市販の試薬を購入して用いることも可能である。
<5 (6) -Amino-2- (4-aminophenyl) benzimidazole (DAPBI) (DAPBI)>
DAPBI (formula (1)) used in the present invention can be produced according to a conventionally known method. It is also possible to purchase and use commercially available reagents.
得られるポリマー溶液の粘度（重合度）を紡糸に適した重合度に制御するためには、熱分析における特定範囲で特定比率の吸熱ピークを有し、特定値以下の水分率のＤＡＰＢＩを用いることが重要となる。 In order to control the viscosity (degree of polymerization) of the resulting polymer solution to a degree of polymerization suitable for spinning, use DAPBI having an endothermic peak with a specific ratio in a specific range in thermal analysis and a moisture content below a specific value. Is important.
第一に、熱分析において、２１０℃〜２３０℃の範囲に観測される第１の吸熱ピーク、および、２３５〜２５０℃の範囲に観測される第２の吸熱ピークを有する。吸熱ピークの位置は、当該ジアミンに由来するものであり、上記の２つの範囲に吸熱ピークを有さない化合物は、異なる化合物となるため好ましくない。 First, the thermal analysis has a first endothermic peak observed in the range of 210 ° C. to 230 ° C. and a second endothermic peak observed in the range of 235 to 250 ° C. The position of the endothermic peak is derived from the diamine, and a compound having no endothermic peak in the above two ranges is not preferable because it becomes a different compound.
本発明においては、このＤＡＰＢＩを、１２０℃以上１８０℃以下、より好ましくは１３０℃以上１６０℃以下の温度範囲にて、窒素雰囲気下において大気圧下３０分以上熱乾燥処理により調整する。乾燥温度が１２０℃未満の場合には、ＤＡＰＢＩ合成の際に混入する水分を１００ｐｐｍ以下に除去することが困難となる。一方で、乾燥温度が１８０℃を超える場合には、ＤＡＰＢＩの変色が起こり、かつ、第２の吸熱ピークが大きくなるため好ましくない。 In the present invention, this DAPBI is adjusted by a heat drying treatment in a temperature range of 120 ° C. or higher and 180 ° C. or lower, more preferably 130 ° C. or higher and 160 ° C. or lower in a nitrogen atmosphere at atmospheric pressure for 30 minutes or longer. When the drying temperature is less than 120 ° C., it is difficult to remove the moisture mixed during the DAPBI synthesis to 100 ppm or less. On the other hand, when the drying temperature exceeds 180 ° C., discoloration of DAPBI occurs and the second endothermic peak becomes large, which is not preferable.
また、上記第１の吸熱ピークと第２の吸熱ピークとの吸熱量の比は、ポリマー溶液の粘度（重合度）を制御するうえで重要である。粘度（重合度）を制御し、均一なコポリアミド溶液を得るためには、第２の吸熱ピークに対する第１の吸熱ピークの比（第１の吸熱ピーク／第２の吸熱ピーク）が０．８以上であることが必要である。０．８未満の場合には、ポリマー溶液の粘度（重合度）が上昇し、紡糸が困難となるため好ましくない。本発明においては、上記の乾燥処理により、第２の吸熱ピークに対する第１の吸熱ピークの比を０．８以上とすることができる。 The ratio of the endothermic amount between the first endothermic peak and the second endothermic peak is important in controlling the viscosity (degree of polymerization) of the polymer solution. In order to control the viscosity (degree of polymerization) and obtain a uniform copolyamide solution, the ratio of the first endothermic peak to the second endothermic peak (first endothermic peak / second endothermic peak) is 0.8. That is necessary. If it is less than 0.8, the viscosity (degree of polymerization) of the polymer solution increases and spinning becomes difficult, which is not preferable. In the present invention, the ratio of the first endothermic peak to the second endothermic peak can be set to 0.8 or more by the above drying treatment.
また、上記ＤＡＰＢＩの含有水分率は、反応性を制御するうえで重要である。重合反応性を高め、ポリマー溶液を紡糸に適した重合度に制御するためには、含有水分率が１００ｐｐｍ以下であることが必要である。１００ｐｐｍを超える場合には、ＤＡＰＢＩの反応性が低下し、ポリマー溶液の粘度（重合度）が制御困難となるため好ましくない。本発明においては、上記の乾燥処理により、第１の吸熱ピークに対する第２の吸熱ピークの比を０．８以上としつつ、含有水分率を１００ｐｐｍ以下とすることができる。 In addition, the moisture content of the DAPBI is important for controlling the reactivity. In order to increase the polymerization reactivity and control the polymer solution to a degree of polymerization suitable for spinning, it is necessary that the water content is 100 ppm or less. When it exceeds 100 ppm, the reactivity of DAPBI decreases, and the viscosity (degree of polymerization) of the polymer solution becomes difficult to control, which is not preferable. In the present invention, the moisture content can be reduced to 100 ppm or less while the ratio of the second endothermic peak to the first endothermic peak is 0.8 or more by the above drying treatment.
以下、本発明を実施例等によりさらに具体的に説明するが、本発明は、その要旨を超えない限り、これに何等限定されるものではない。 EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, this invention is not limited to this unless it exceeds the summary.
＜測定・評価方法＞
実施例および比較例においては、以下の項目について、以下の方法によって測定・評価を実施した。
<Measurement and evaluation method>
In Examples and Comparative Examples, the following items were measured and evaluated by the following methods.
（１）熱分析
ＤＳＣ（ティー・エイ・インスツルメント社製、型式：Ｑ−１０）を用いて、窒素雰囲気下にて、下記の条件で昇温させた際の５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール（ＤＡＰＢＩ）と基準物質との温度差を測定することにより、吸熱ピークおよび吸熱量を算出した。
［測定条件］
測定範囲 ：６０〜２６０℃
昇温速度 ：２０℃／ｍｉｎ
サンプル量 ：２０ｍｇ
基準物質 ：酸化アルミニウム
(1) Thermal analysis 5 (6) -Amino- when DSC (manufactured by TA Instruments Inc., model: Q-10) was heated under the following conditions under a nitrogen atmosphere. An endothermic peak and an endothermic amount were calculated by measuring a temperature difference between 2- (4-aminophenyl) benzimidazole (DAPBI) and a reference substance.
[Measurement condition]
Measurement range: 60-260 ° C
Temperature increase rate: 20 ° C / min
Sample amount: 20mg
Reference material: Aluminum oxide
（２）水分率
カールフィッシャー水分計（京都電子工業株式会社製、型式：ＭＫＳ−５００）を用いて、５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール（ＤＡＰＢＩ）ＮＭＰ溶液中の水分を下記の条件で滴定することにより、水分率を算出した。
［測定条件］
滴定溶液 ：ハイドラナール・コンポジット５（シグマアルドリッチ社製）
測定温度 ：２５℃
サンプル量 ：１０ｍｇ
(2) Moisture content In a 5 (6) -amino-2- (4-aminophenyl) benzimidazole (DAPBI) NMP solution using a Karl Fischer moisture meter (Kyoto Electronics Industry Co., Ltd., model: MKS-500). The water content was calculated by titrating the water under the following conditions.
[Measurement condition]
Titration solution: Hydranal Composite 5 (manufactured by Sigma-Aldrich)
Measurement temperature: 25 ° C
Sample amount: 10mg
（３）紡糸性
コポリアミド溶液を半乾半湿式紡糸により凝固液中に押し出し、ドラフト率２．４倍にて凝固液から凝固糸として引き取り、下記の判定基準により、１０分間における単糸切れの発生状況を判定した。
［判定基準］
良好 ：１０分間観測し単糸切れ発生無し
不良 ：１０分間観測し単糸切れ１本以上発生
不可 ：流動性が低下し紡糸できず
(3) Spinnability The copolyamide solution is extruded into the coagulation liquid by semi-dry and semi-wet spinning, taken as coagulated yarn from the coagulation liquid at a draft rate of 2.4 times, and the single yarn breakage in 10 minutes is determined according to the following criteria. The occurrence status was judged.
[Criteria]
Good: Observed for 10 minutes, no single yarn breakage Poor: Observed for 10 minutes, one or more single yarn breaks occurred Impossible: Fluidity decreased and spinning failed
＜実施例１＞
［５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール（ＤＡＰＢＩ）の調製］
熱分析において２１５℃に観測される第１の吸熱ピークと２３５℃に観測される第２の吸熱ピークとを有する、５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール（ＤＡＰＢＩ）を、窒素雰囲気下において大気圧で１５０℃、３０分乾燥することにより、ＤＡＰＢＩの調整を行った。調製後のＤＡＰＢＩの熱分析においては、第１の吸熱ピークは２２３℃、第２の吸熱ピークは２４０℃に観測され、かつ第２の吸熱ピークに対する第１の吸熱ピークの比が０．９であり水分率は６８ｐｐｍであった。
<Example 1>
[Preparation of 5 (6) -amino-2- (4-aminophenyl) benzimidazole (DAPBI)]
5 (6) -amino-2- (4-aminophenyl) benzimidazole (DAPBI) having a first endothermic peak observed at 215 ° C. and a second endothermic peak observed at 235 ° C. in thermal analysis. The DAPBI was adjusted by drying at 150 ° C. for 30 minutes under a nitrogen atmosphere at atmospheric pressure. In the thermal analysis of DAPBI after preparation, the first endothermic peak is observed at 223 ° C., the second endothermic peak is observed at 240 ° C., and the ratio of the first endothermic peak to the second endothermic peak is 0.9. The moisture content was 68 ppm.
［芳香族ポリアミドの製造］
塩化カルシウムを、窒素を内部にフローしている乾燥容器に入れて乾燥させた。乾燥させた塩化カルシウム粉末１６０ｇとＮ−メチル−２−ピロリドン（ＮＭＰ）１．６１８Ｌとを、窒素フローしている攪拌翼を有する攪拌槽に投入した後、ＮＭＰに塩化カルシウム粉末を溶解した。
次いで、パラフェニレンジアミン１０．２ｇ（ジアミン全体に対して３０ｍｏｌ％）と、上記で調整したＤＡＰＢＩ４９．１ｇ（ジアミン全体に対して７０ｍｏｌ％）とを、攪拌槽に投入して溶解した。
続いて、テレフタル酸クロライド６２．３ｇ（加えたジアミンのモル量に対して９８．０ｍｏｌ％）を投入して反応せしめることにより、芳香族コポリアミド溶液を得た。
さらに、得られた芳香族コポリアミド溶液に、２２．５質量％の水酸化カルシウムを含有するＮＭＰ分散液１００．４ｇを添加して、中和反応を行った。
[Production of aromatic polyamide]
The calcium chloride was dried in a drying container with nitrogen flowing inside. After 160 g of dried calcium chloride powder and 1.618 L of N-methyl-2-pyrrolidone (NMP) were put into a stirring tank having a stirring blade in which nitrogen was flowing, the calcium chloride powder was dissolved in NMP.
Next, 10.2 g of paraphenylenediamine (30 mol% with respect to the entire diamine) and 49.1 g of DAPBI prepared as described above (70 mol% with respect to the entire diamine) were charged into a stirring vessel and dissolved.
Subsequently, 62.3 g of terephthalic acid chloride (98.0 mol% with respect to the molar amount of the added diamine) was added and reacted to obtain an aromatic copolyamide solution.
Furthermore, 100.4 g of NMP dispersion containing 22.5% by mass of calcium hydroxide was added to the obtained aromatic copolyamide solution to carry out a neutralization reaction.
［芳香族コポリアミド繊維の紡糸］
上記で得られた芳香族コポリアミド溶液を用いて、孔径０．１５ｍｍ、孔数２４ホールの紡糸口金から、毎分３．５ｃｃの割合で吐出し、エアーギャップと呼ばれる空隙部分を介して、ＮＭＰと水とからなる凝固液（ＮＭＰ濃度：４０質量％、温度：５０℃）中に紡出し、凝固糸を得た。なお、凝固糸を引き取る際のドラフト率は、２．４倍とした。
このときの芳香族コポリアミド溶液の紡糸性は、良好であった。測定および評価結果を、表１に示す。
[Spinning of aromatic copolyamide fiber]
Using the aromatic copolyamide solution obtained above, NMP was discharged from a spinneret having a pore diameter of 0.15 mm and a hole number of 24 holes at a rate of 3.5 cc per minute, and through an air gap called an air gap. Spinning into a coagulation liquid (NMP concentration: 40 mass%, temperature: 50 ° C.) composed of water and water, a coagulated yarn was obtained. In addition, the draft rate at the time of taking out the coagulated yarn was 2.4 times.
The spinnability of the aromatic copolyamide solution at this time was good. The measurement and evaluation results are shown in Table 1.
＜比較例１＞
ＤＡＰＢＩ調製時の乾燥温度を１００℃とした以外は、実施例１と同様にして芳香族コポリアミド溶液を重合した。
調製後のＤＡＰＢＩの水分率は３２０ｐｐｍであり、得られた芳香族コポリアミド溶液の紡糸性は不良であった。測定および評価結果を、表１に示す。
<Comparative Example 1>
The aromatic copolyamide solution was polymerized in the same manner as in Example 1 except that the drying temperature during the preparation of DAPBI was 100 ° C.
The moisture content of DAPBI after preparation was 320 ppm, and the spinnability of the obtained aromatic copolyamide solution was poor. The measurement and evaluation results are shown in Table 1.
＜比較例２＞
熱分析において２４０℃に観測される第２の吸熱ピークのみを有し、このため、第２の吸熱ピークに対する第１の吸熱ピークの比が０である、５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール（ＤＡＰＢＩ）を用いた以外は、実施例１と同様にして芳香族コポリアミドを重合した。しかしながら、生成したコポリアミドが析出して溶液とならないため、繊維を得ることができなかった。測定および評価結果を、表１に示す。
<Comparative Example 2>
It has only a second endothermic peak observed at 240 ° C. in the thermal analysis, so that the ratio of the first endothermic peak to the second endothermic peak is 0, 5 (6) -amino-2- ( An aromatic copolyamide was polymerized in the same manner as in Example 1 except that 4-aminophenyl) benzimidazole (DAPBI) was used. However, since the produced copolyamide is deposited and does not form a solution, fibers cannot be obtained. The measurement and evaluation results are shown in Table 1.
＜比較例３＞
熱分析において２４０℃に観測される第２の吸熱ピークのみを有し、このため、第２の吸熱ピークに対する第１の吸熱ピークの比が０である、５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール（ＤＡＰＢＩ）を用いた以外は、比較例１と同様にして芳香族コポリアミドを重合した。
調製後のＤＡＰＢＩの水分率は８０５ｐｐｍであり、得られた芳香族コポリアミド溶液の紡糸性は不良であった。測定および評価結果を、表１に示す。
<Comparative Example 3>
It has only a second endothermic peak observed at 240 ° C. in the thermal analysis, so that the ratio of the first endothermic peak to the second endothermic peak is 0, 5 (6) -amino-2- ( An aromatic copolyamide was polymerized in the same manner as in Comparative Example 1 except that 4-aminophenyl) benzimidazole (DAPBI) was used.
The moisture content of the prepared DAPBI was 805 ppm, and the spinnability of the obtained aromatic copolyamide solution was poor. The measurement and evaluation results are shown in Table 1.
＜比較例４＞
ＤＡＰＢＩ調製時の乾燥温度を１９０℃とした以外は、実施例１と同様にして芳香族コポリアミド溶液を重合した。しかしながら、生成したコポリアミドが析出して溶液とならないため、繊維を得ることができなかった。測定および評価結果を、表１に示す。
<Comparative example 4>
The aromatic copolyamide solution was polymerized in the same manner as in Example 1 except that the drying temperature during preparation of DAPBI was 190 ° C. However, since the produced copolyamide is deposited and does not form a solution, fibers cannot be obtained. The measurement and evaluation results are shown in Table 1.
＜比較例５＞
熱分析において２２６℃に観測される第１の吸熱ピークと２３８℃に観測される第２の吸熱ピークとを有し、第２の吸熱ピークに対する第１の吸熱ピークの比が０．５である、５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール（ＤＡＰＢＩ）を用いた以外は、実施例１と同様にして芳香族コポリアミド溶液を重合した。しかしながら、コポリアミド溶液の流動性が低下し、紡糸性は不良であった。測定および評価結果を、表１に示す。
<Comparative Example 5>
In the thermal analysis, it has a first endothermic peak observed at 226 ° C. and a second endothermic peak observed at 238 ° C., and the ratio of the first endothermic peak to the second endothermic peak is 0.5. The aromatic copolyamide solution was polymerized in the same manner as in Example 1 except that 5 (6) -amino-2- (4-aminophenyl) benzimidazole (DAPBI) was used. However, the fluidity of the copolyamide solution was lowered and the spinnability was poor. The measurement and evaluation results are shown in Table 1.
Claims (2)
含有水分率が１００ｐｐｍ以下である５（６）−アミノ−２−（４−アミノフェニル）ベンジミダゾール（式（１））。
5 (6) -amino-2- (4-aminophenyl) benzimidazole (formula (1)) having a water content of 100 ppm or less.
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