JPS6399231A - Soluble and heat-resistant copolyamide - Google Patents
Soluble and heat-resistant copolyamideInfo
- Publication number
- JPS6399231A JPS6399231A JP4768887A JP4768887A JPS6399231A JP S6399231 A JPS6399231 A JP S6399231A JP 4768887 A JP4768887 A JP 4768887A JP 4768887 A JP4768887 A JP 4768887A JP S6399231 A JPS6399231 A JP S6399231A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- copolyamide
- bis
- aminophenyl
- dimethylacetamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims 1
- 238000000691 measurement method Methods 0.000 claims 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 abstract description 10
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 abstract description 3
- 150000004985 diamines Chemical class 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract 4
- LYXAQAXLWMRPOZ-UHFFFAOYSA-N 2-[1-(2-aminophenyl)-9h-fluoren-2-yl]aniline Chemical class NC1=CC=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=CC=C1N LYXAQAXLWMRPOZ-UHFFFAOYSA-N 0.000 abstract 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000004952 Polyamide Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 8
- 239000004760 aramid Substances 0.000 description 6
- 229920003235 aromatic polyamide Polymers 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- -1 Poly(p-phenylene terephthalamide) Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000004953 Aliphatic polyamide Substances 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 229920003231 aliphatic polyamide Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- YRKVLGUIGNRYJX-UHFFFAOYSA-N 4-[9-(4-amino-3-methylphenyl)fluoren-9-yl]-2-methylaniline Chemical compound C1=C(N)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(N)=CC=2)=C1 YRKVLGUIGNRYJX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- NVEGKMMBAINHFN-UHFFFAOYSA-N prop-1-ene;terephthalic acid Chemical group CC=C.OC(=O)C1=CC=C(C(O)=O)C=C1 NVEGKMMBAINHFN-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、新規な高共重合ポリアミド（以下コポリアミ
ドという、）であって、＃熱性及び溶解性を有しており
、繊維及びフィルム、成形物の素材として使用可能なコ
ポリアミドに関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is a novel highly copolymerized polyamide (hereinafter referred to as copolyamide), which has thermal properties and solubility, and is suitable for use in fibers, films, and molded articles. Regarding copolyamides that can be used as materials for.
従来の技術
一般に脂肪族系ポリアミドは繊維にした場合、優秀な繊
維として衣料などに巾広く用いられている。しかしなが
ら、脂肪族ポリアミドｍ維は伸度は大きいが、芳香族ポ
リアミドｍ維に比べて、強度、弾性率が低く、また耐熱
性に劣るため、その用途が限定されている。BACKGROUND OF THE INVENTION In general, aliphatic polyamides are excellent fibers and are widely used in clothing and the like. However, although aliphatic polyamide m-fibers have high elongation, their use is limited because they have lower strength, lower elastic modulus, and inferior heat resistance than aromatic polyamide m-fibers.
一方、全芳香族ポリアミドは高い軟化点及び融点を右１
２、高温時の強度維持率などの耐熱性や強度ｔｉ性率の
機械的特性は極めて良好である。しかしながら、繊維と
した場合、伸度が５％未満と低いばかりでなく、繊維自
体がフィブリル化して、幾筋にも割れる恐れがある。こ
の理由は芳香族ポリアミドを液晶紡糸によって製造され
た繊維であることに起因すると考えられる。On the other hand, fully aromatic polyamides have high softening and melting points.
2. Heat resistance such as strength retention rate at high temperatures and mechanical properties such as strength ti ratio are extremely good. However, when made into fibers, not only do they have a low elongation of less than 5%, but the fibers themselves may become fibrillated and crack into multiple lines. This is thought to be due to the fact that the fibers are produced from aromatic polyamide by liquid crystal spinning.
また、コルシャックらはジャーナル・オブＯマクロモＬ
／キュル・サイエンス（Ｊ、 Ｍａｅｒｏｍｏｌ、 Ｓ
ｃｉ、。Additionally, Korshak et al.
/ Cur Science (J, Maeromol, S
ci,.
Ｒｅｖ、 ＭａｃｒｏＩｌｏｌ、 Ｃｈｅ＋＊、、 ０
１１ 、４５．１９７４年）に可溶性ポリアミドについ
て報告しているが、この報告には可溶性及び成形性の両
方の特性を備えた例は示されてはいない。Rev, MacroIlol, Che++,, 0
11, 45. (1974) reported on soluble polyamides, but this report does not provide any examples having both the properties of solubility and moldability.
発明が解決しようとする問題点
一般的に大きな剛直性や高い対称性を有する芳香族ポリ
アミドは、優れた機械的特性を有する反面、融点が高く
、しかも分解点に近いので、溶融成形は困難である。さ
らに溶解性が劣り、工業材料としての使用が容易でない
欠点を有する。Problems to be Solved by the Invention Although aromatic polyamides, which generally have great rigidity and high symmetry, have excellent mechanical properties, they have a high melting point and are close to the decomposition point, making it difficult to melt mold. be. Furthermore, it has the disadvantage of poor solubility, making it difficult to use as an industrial material.
代表的な芳香族ポリアミドであるポリ（ｐ−フェニレン
テレフタルアミド）は、濃硫酸または塩化リチウム、塩
化カルシウム等を溶解したヘキサメチルホスホリルアミ
ドあるいはＮ−メチルピロリドンなどには溶解するが、
なお溶解性が低いので溶液として使用し難い欠点がある
。Poly(p-phenylene terephthalamide), a typical aromatic polyamide, is soluble in concentrated sulfuric acid or hexamethylphosphorylamide or N-methylpyrrolidone in which lithium chloride, calcium chloride, etc. are dissolved.
However, it has the disadvantage that it is difficult to use as a solution because of its low solubility.
また、脂肪族ポリアミドは＃熱性が劣り、さらに一部芳
香族化したポリテレフタル酸アミドであっても耐熱性は
十分ではない０例えば、アミン成分として、ヘキサメチ
レンジアミンやプロピレンジアミンを用いた場合、耐熱
性ばかりでなく溶解性にも問題点がある。In addition, aliphatic polyamides have poor heat resistance, and even partially aromatic polyterephthalic acid amide does not have sufficient heat resistance.For example, when hexamethylene diamine or propylene diamine is used as the amine component, There are problems not only in heat resistance but also in solubility.
また、溶解性の向上はフィルムやＨｈ雄に加工すること
は容易となるが、機械、電気関係の部品等に使用する場
合の成形物加工には適していないゆここで熱を利用した
成形物加工法を利用しうる条件として、高過ぎないガラ
ス転移温度（７ｇ）、即ち、 ４００℃以下のＴｇを持
つことが要求される。In addition, improved solubility makes it easier to process into films and Hh male, but molded products using heat are not suitable for processing molded products for use in machinery, electrical parts, etc. As a condition for using the processing method, it is required that the glass transition temperature (7g) is not too high, that is, the Tg is 400°C or less.
本発明は、芳香族ポリアミドと脂肪族ポリアミドの欠点
を補完し、ポリアミドの溶解性と高＃熱性、さらに熱を
利用した成形加工性を兼ね備えたコポリアミドを提供す
るものである。The present invention compensates for the drawbacks of aromatic polyamides and aliphatic polyamides, and provides a copolyamide that has both the solubility and high thermal properties of polyamides, as well as moldability using heat.
問題点を解決干るための手段・作用
すなわち１本発明は式＋Ｘ−ＮＨ−Ｙ−ＮＨ）で示Ｒは
Ｈ、ＣＨ３，Ｃ２Ｈ５からなる群から選ばれたいずれか
である。）及び式（（：） −ＣｎＨ２ｎ −（但し、
式中ｎは２〜８の正数である。）の鎖員からなるコポリ
アミドであり、且つ前記コポリアミド０．５ｇをジメチ
ルアセトアミド１００−に溶解した溶液を３０℃で測定
した固有粘度（ηｉｎｈ）が０．２５ ｄｌ ／ｇ以上
である可溶性耐熱コポリアミドである。Means and Actions for Solving the Problems (1) The present invention is represented by the formula +X-NH-Y-NH), where R is one selected from the group consisting of H, CH3, and C2H5. ) and the formula ((:) -CnH2n - (however,
In the formula, n is a positive number from 2 to 8. ) is a copolyamide consisting of chain members of It is a copolyamide.
式中Ｘを構成する式（Ａ）の原料としては、テレフタル
酸クロリド、イソフタル酸クロリド等であり、式中Ｙを
構成する式（Ｂ）の原料としては。Examples of the raw material of formula (A) constituting X in the formula include terephthalic acid chloride, isophthalic acid chloride, etc., and raw materials of formula (B) constituting Y in the formula.
９．９−ビス（４−７ミノフエニル）フルオレン、９，
９−ビス（３−メチル−４−アミノフェニル）フルオレ
ン、９．９−ビス（３−エチル−４−アミノフェニル）
フルオレン、等でアリ、式（Ｃ）の原料としてはメチレ
ンジアミン、１．２−エチレンジアミン、ｌ、３−プロ
ピレンジアミン、１．４−ブチレンジアミン、１．５−
ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘ
プタメチレンジアミン、オクタメチレンジアミン等があ
げられる。9.9-bis(4-7minophenyl)fluorene, 9,
9-bis(3-methyl-4-aminophenyl)fluorene, 9.9-bis(3-ethyl-4-aminophenyl)
Fluorene, etc., and raw materials for formula (C) include methylene diamine, 1,2-ethylene diamine, 1,3-propylene diamine, 1,4-butylene diamine, 1,5-
Examples include pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, and octamethylene diamine.
式（Ｃ）のｎが２〜８の正数の場合が、耐熱性を保持し
つつ溶解性、成形加工性を向上することができる。When n in formula (C) is a positive number of 2 to 8, solubility and moldability can be improved while maintaining heat resistance.
これらの原料のうちでも好ましいものは、式（Ａ）では
テレフタル酸クロリドであり、式（Ｃ）ではＴ業的に生
産され、より安価な１．３−プロピレンジアミン、ヘキ
サメチレンジアミンであり、最も好ましくは１．３−プ
ロピレンジアミンである。Preferred among these raw materials are terephthalic acid chloride in formula (A), and 1,3-propylene diamine and hexamethylene diamine, which are commercially produced and cheaper in formula (C), and the most preferred. Preferably it is 1,3-propylene diamine.
また式中Ｙは鎖員式（Ｂ）成分と式（Ｃ）成分とからな
るが、両者の割合は、生成するコポリアミドの溶解性に
関係するため、（Ｂ）と（Ｃ）のモル比としては６０
： ４０〜９９：ｌとすることが望ましい。Furthermore, in the formula, Y consists of a chain member formula (B) component and a formula (C) component, and since the ratio of both is related to the solubility of the copolyamide to be produced, the molar ratio of (B) and (C) is 60 as
: It is desirable to set it as 40-99:l.
すなわち、本発明のコポリアミドの鎖員式（Ｃ）のモル
比が４０を越えるようになると、溶解性が低下する。例
えば、テレフタル酸クロリドと９，９−ビス（４−アミ
ノフェニル）フルオレン、それにヘキサメチレンジアミ
ンまたはプロピレンジアミンを所定量用い、ジメチルア
セトアミドまたはＮ−メチルピロリドン中で重合を行う
際に、途中より、コポリアミドが析出してしまい、高重
合度のコポリアミドを得ることが困難になる。さらにコ
ポリアミド末端は未処理のままでもよいが、好ましくは
アミノ基をアシル化等を行うことにより、酸化され難い
工夫がなされる。このアシル基はアセチル基またはベン
ゾイル基が適している。That is, when the molar ratio of the chain member formula (C) of the copolyamide of the present invention exceeds 40, the solubility decreases. For example, when polymerizing terephthalic acid chloride, 9,9-bis(4-aminophenyl)fluorene, and hexamethylene diamine or propylene diamine in predetermined amounts in dimethylacetamide or N-methylpyrrolidone, some polymerization may occur during polymerization. The polyamide will precipitate, making it difficult to obtain a copolyamide with a high degree of polymerization. Further, the copolyamide terminals may be left untreated, but preferably the amino groups are acylated to make them less susceptible to oxidation. This acyl group is suitably an acetyl group or a benzoyl group.
本発明のコポリアミドの製造方法としては、９．９−ビ
ス（４−７ミノフエニル）フルオレンとジアミンさらに
トリエチルアミン等をジメチルアセトアミド等の溶媒に
溶かし、５℃程度の低温に冷却下、テレフタル酸クロリ
ドを徐々に加え、２時間程度反応させることにより得ら
れる。同様の反応条件で種々のジアミン、ジカルボン酸
を用いて合成を行なうことができる。The method for producing the copolyamide of the present invention involves dissolving 9,9-bis(4-7minophenyl)fluorene, diamine, triethylamine, etc. in a solvent such as dimethylacetamide, cooling to a low temperature of about 5°C, and adding terephthalic acid chloride. It is obtained by adding it gradually and reacting for about 2 hours. Synthesis can be carried out using various diamines and dicarboxylic acids under similar reaction conditions.
また本発明の上記コポリアミドはこのコポリアミド０．
５ｇをジメチルアセトアミド１００−に溶解した溶液を
３０℃で測定した値に基づく固有粘度（ηｉｎｈ）は、
このコポリアミドの機械物性の強度より０．２５ ｄｌ
ｌ ／ｇ以上であることが必要であり、特に０．３０ｄ
ｌｌ ／ｇ以上のものが好適である。また、ガラス転移
温度（７ｇ）はコポリアミドの耐熱性と熱的成形加工の
容易さから、４００℃以下、好ましくは２００〜４００
℃である。さらにこのコポリアミドは少なくともピリジ
ン、ｍ−クレゾール、０−クロルフェノール、Ｎ−メチ
ルピロリドン、ジメチルアセトアミドに溶解するもので
ある。Further, the above-mentioned copolyamide of the present invention is made of this copolyamide 0.
The intrinsic viscosity (ηinh) based on the value measured at 30°C of a solution of 5g dissolved in 100-dimethylacetamide is:
0.25 dl from the mechanical strength of this copolyamide
l /g or more, especially 0.30d
ll/g or more is preferable. In addition, the glass transition temperature (7g) is 400°C or less, preferably 200 to 400°C, due to the heat resistance of copolyamide and the ease of thermal molding.
It is ℃. Furthermore, this copolyamide is soluble in at least pyridine, m-cresol, 0-chlorophenol, N-methylpyrrolidone, and dimethylacetamide.
そしてコポリアミドを前記の溶剤に溶かし、繊維または
フィルムとした場合、無着色、透明のものが得られる。When the copolyamide is dissolved in the above-mentioned solvent and made into fibers or films, uncolored and transparent products can be obtained.
本発明により提供されるコポリアミドは、無着色で溶解
性及び耐熱性が従来品に比べて向上しており、機械的特
性及び電気特性も良好である。かつガラス転移温度の調
節が可能で熱的成形加工も容易である。The copolyamide provided by the present invention is uncolored, has improved solubility and heat resistance compared to conventional products, and also has good mechanical and electrical properties. In addition, the glass transition temperature can be adjusted and thermal molding is easy.
以下実施例に基づいてさらに詳細に説明する。A more detailed explanation will be given below based on examples.
実施例
実施例１
９１．９−ビス（４−アミノフェニル）フルオレン（Ａ
Ｆ）４．１８ ｇ 、 １．３−プロピレンジアミン
（ＰＤＡ）０．５９ｇとトリエチルアミン４．０４ｇを
、ジメチルアセトアミド＋００−に溶解し、５℃に冷却
下攪拌しながら、テレフタル酸クロリド４．０８ｇ （
粉末状）を徐々に加えた。３時間攪拌後１反応によって
副生じたトリエチルアミン塩酸塩を濾別し、濾液をメタ
ノール中に注ぎポリマーを再沈した。さらにこれを痘過
して得たコポリアミドの加熱乾燥を行なって、目的物を
得た。その収率は１００％であった。Examples Example 1 91.9-bis(4-aminophenyl)fluorene (A
F) 4.18 g, 0.59 g of 1,3-propylene diamine (PDA) and 4.04 g of triethylamine were dissolved in dimethylacetamide +00-, and while stirring while cooling to 5°C, 4.08 g of terephthalic acid chloride (
(powder) was gradually added. After stirring for 3 hours, triethylamine hydrochloride produced as a by-product from one reaction was filtered off, and the filtrate was poured into methanol to reprecipitate the polymer. Furthermore, the copolyamide obtained by sieving this was heat-dried to obtain the desired product. The yield was 100%.
得られたコポリアミドの赤外線吸収スペクトルはＮＨの
吸収が３２５０ｃｍ−’、アミドカルボニル基の吸収が
１８８０ｃ＋ｗ−’、脂肪族の吸収が３０００〜２Ｂ５
０ｃ曽−’ テあり、また芳香族の吸収が３２００〜３
０００ｃｍ−’、１６２０Ｃ■″″１〜１５１０ｃｍ−
’にあり、ポリアミドの特性吸収を示した。The infrared absorption spectrum of the obtained copolyamide shows that the absorption of NH is 3250cm-', the absorption of amide carbonyl group is 1880c+w-', and the absorption of aliphatic is 3000-2B5.
0c so-' Te is present, and aromatic absorption is 3200~3
000cm-', 1620C■''''1~1510cm-
', and showed the characteristic absorption of polyamide.
また、９．９−ビス（４−アミノフェニル）フルオレン
５．５７ｇ、１．３−プロピレンジアミン０．３０ｇと
仕込量を変えた以外は実施例１と全く同様に重合を行な
った。Further, polymerization was carried out in exactly the same manner as in Example 1 except that the amounts charged were changed to 5.57 g of 9.9-bis(4-aminophenyl)fluorene and 0.30 g of 1.3-propylene diamine.
得られたコポリアミドの特性を第１表に示した。第１表
中には、比較のため、９．９−ビス（４−アミノフェニ
ル）フルオレン４．１８ｇとテレフタル酸クロリドから
得られたポリアミドの特性を比較例として示した。The properties of the obtained copolyamide are shown in Table 1. For comparison, Table 1 shows the properties of a polyamide obtained from 4.18 g of 9,9-bis(4-aminophenyl)fluorene and terephthalic acid chloride as a comparative example.
実施例２
９．９−ビス（４−アミノフェニル）フルオレン４．１
８ｇ、１．３−プロピレンシフ ミ７０．５８ｇとトリ
エチルアミン４．０４ ｇをジメチルアセトアミド１０
０−に溶解し、５℃に冷却下、攪拌しながらテレフタル
酸クロリド４．０６ｇを粉末のまま徐々に加えた。２時
間後、塩化ベンゾイル０．５ｗ＋４１を加え、室温で２
時間攪拌した。副生じたトリエチルアミン塩酸塩を濾別
後、癌液をメタノール中に注ぎ析出したポリマーを濾過
、洗浄し、さらに加熱乾燥して目的のコポリアミドを得
た。その収率は８９％であった。Example 2 9.9-bis(4-aminophenyl)fluorene 4.1
8 g, 70.58 g of 1,3-propylene Schiff and 4.04 g of triethylamine were mixed with 10 g of dimethylacetamide.
4.06 g of terephthalic acid chloride was gradually added as a powder while stirring and cooling to 5°C. After 2 hours, add 0.5w+41 benzoyl chloride, and add 2 hours at room temperature.
Stir for hours. After filtering off the by-produced triethylamine hydrochloride, the cancer liquid was poured into methanol, and the precipitated polymer was filtered, washed, and further heated and dried to obtain the desired copolyamide. The yield was 89%.
得られたコポリアミドの赤外線吸収スペクトルは、ＮＨ
の吸収が３２４０ｃｍ−’、３２００〜３０００ｃｍ’
″１に芳香族、３０００〜２９００ｃｍ−’に脂肪族の
吸収、１６８０ｃｍ−’にアミドカルボニル、１６１０
．１５３０ｃｍ−’に芳香族の吸収を示した。The infrared absorption spectrum of the obtained copolyamide is NH
absorption of 3240cm-', 3200-3000cm'
Aromatic absorption at 1, aliphatic absorption at 3000-2900 cm-', amide carbonyl at 1680 cm-', 1610
．． It showed an aromatic absorption at 1530 cm-'.
また、９．９−ビス（４−７ミノフエニル）フルオレン
５．５７ ｇ、１．３−プロピレンジアミン０．３０ｇ
とした以外は実施例２と同様に重合を行なった。Also, 5.57 g of 9.9-bis(4-7minophenyl)fluorene, 0.30 g of 1.3-propylene diamine
Polymerization was carried out in the same manner as in Example 2 except that.
得られたコポリアミドの特性を第１表に示した。The properties of the obtained copolyamide are shown in Table 1.
実施例３
９．９−ビス（４−アミノフェニル）フルオレン（ＡＦ
）８．２８ ｇ、ヘキサメチレンジアミン（ＨにＤＡ）
０、１２ ｇとトリエチルアミン４．０４ｇを、ジメチ
ルアセトアミド１００シに溶かし、５℃に冷却下、テレ
フタル酸クロリド４．０６１：を徐々に加えた。、２時
間反応後、副生じたトリエチルアミン塩酸ｊ■を繞別後
、メタノール中に反応液を注いだ。析出したコポリアミ
ドを徳過し、加熱、乾燥した。Example 3 9.9-bis(4-aminophenyl)fluorene (AF
) 8.28 g, hexamethylene diamine (DA to H)
0.12 g of triethylamine and 4.04 g of triethylamine were dissolved in 100 g of dimethylacetamide, and 4.061 g of terephthalic acid chloride was gradually added while cooling to 5°C. After 2 hours of reaction, the triethylamine hydrochloride produced as a by-product was removed, and the reaction solution was poured into methanol. The precipitated copolyamide was filtered, heated and dried.
得られたコポリアミドの特性を第２表に示した。尚第２
表中には、比較のため、ヘキサメチレンジアミンとテレ
フタル酸クロリドから得られたポリアミドの特性を示し
た。The properties of the obtained copolyamide are shown in Table 2. Furthermore, the second
For comparison, the table shows the properties of polyamide obtained from hexamethylene diamine and terephthalic acid chloride.
実施例４
９．９−ビス（４−アミノフェニル）フルオレン８．２
８ｇ、ヘキサメチレンジアミン０．１２ｇとトリエチル
アミン４．０４ ｇを、ジメチルアセトアミド１００−
に溶かし、５℃で２時間反応後、塩化ベンゾイル０．５
−を加え、室温で２時間攪拌した。副生じたトリエチル
アミン塩酸塩を濾別後、濾液をメタ／−ル中に注ぎ析出
したコポリアミドを濾過し、加熱乾燥を行った。また、
９．９−ビス（４−アミノフェニル）フルオレンとへキ
サメチレンジアミンの仕込量を第３表Ｎｏ、■以下のよ
うに変えて同様の反応を行なった。尚Ｎｏ、■以下は本
発明の範囲外の比較例である。Example 4 9.9-bis(4-aminophenyl)fluorene 8.2
8 g, hexamethylene diamine 0.12 g and triethylamine 4.04 g, dimethylacetamide 100-
After reacting at 5°C for 2 hours, 0.5% of benzoyl chloride was dissolved in
- was added and stirred at room temperature for 2 hours. After filtering off the triethylamine hydrochloride produced as a by-product, the filtrate was poured into methanol, and the precipitated copolyamide was filtered and dried by heating. Also,
9. The same reaction was carried out by changing the amounts of 9-bis(4-aminophenyl)fluorene and hexamethylenediamine as shown in Table 3, No. Note that No. 2 and following are comparative examples outside the scope of the present invention.
これらの結果は第２表に、溶解性及び耐熱性等をまとめ
て示した。These results are summarized in Table 2, including solubility and heat resistance.
実施例３．４で得られたコポリアミドの赤外線吸収スペ
クトルは３３００ｃｍ−’にＮＨ１３２００〜３０００
ｃｍ−’に芳香族、３０００〜２８００ｃｍ−’に脂肪
族、１６８０〜１６７０Ｃｆｆｉ”にアミドカルボニル
、１６１０．１５００ｃｍ−’に芳香族の吸収が各々み
ちれた。The infrared absorption spectrum of the copolyamide obtained in Example 3.4 is NH13200-3000 at 3300 cm-'.
cm-' was full of aromatic absorption, 3000 to 2800 cm-' was full of aliphatic absorption, 1680 to 1670 cm-' was full of amide carbonyl absorption, and 1610.1500 cm-' was full of aromatic absorption.
本発明の実施例の表に示す固有粘度は、得られたコポリ
アミド０．５ｇをジメチルアセトアミド１００シに溶解
し、３０℃で測定し固有粘度（ηｉｎｈ）を求めた。ま
た、本発明の実施例に示すガラス転移温度および赤外線
吸収スペクトルはフィルムとして測定した。尚、フィル
ム化はジメチルアセトアミド等に溶解し、薄膜作成した
ものを用いた。The intrinsic viscosity (ηinh) shown in the table of Examples of the present invention was determined by dissolving 0.5 g of the obtained copolyamide in 100 g of dimethylacetamide and measuring at 30°C. Further, the glass transition temperature and infrared absorption spectrum shown in the examples of the present invention were measured as a film. For film formation, a thin film prepared by dissolving in dimethylacetamide or the like was used.
薄膜作成は容易に行えた。Thin film creation was easy.
（以下余白）
発明の効果
本発明のコポリアミドは、従来のテレフタル酸−ヘキサ
メチレンジアミン系またはテレフタル酸−プロピレンジ
アミン系ポリアミドに比べ耐熱性及び溶解性が向上した
ものであるので、その利用範囲や加工法が広がり、より
巾広く利用しうるちのである。即ち、ガラス転移温度の
降下により、熱圧１ｉｉ！＆形が可能となり、成形物へ
の加工の道が開かれ、溶解性よりのフィルム化の道と合
わせて、利用範囲が大きく開かれる。特に電気、′ｌ！
ｌ甘子として大いに期待できる。(Left below) Effects of the Invention The copolyamide of the present invention has improved heat resistance and solubility compared to conventional terephthalic acid-hexamethylene diamine-based or terephthalic acid-propylene diamine-based polyamides. Processing methods have expanded, and Uruchino has become more widely available. That is, due to the decrease in glass transition temperature, the thermal pressure is 1ii! & shape, opening the way to processing into molded products, and together with the path to film formation from dissolution, the range of use will be widened. Especially electricity,'l!
I have high hopes for her as Amako.
Claims (3)
を有し、その式中Ｘが式（Ａ）▲数式、化学式、表等が
あります▼であり、Ｙが式（Ｂ）▲数式、化学式、表等
があります▼（但し、式中Ｒは Ｈ、ＣＨ＿３、Ｃ＿２Ｈ＿５からなる群より選ばれたい
ずれかである。）及び式（Ｃ）−ＣｎＨ＿２＿ｎ−（但
し、式中ｎは２〜８の正数である。）の鎖員からなるコ
ポリアミドであり、且つ前記コポリアミド０．５ｇをジ
メチルアセトアミド１００ｍｌに溶解した溶液を３０℃
で測定した固有粘度（ηｉｎｈ）が０．２５ｄｌ／ｇ以
上である可溶性耐熱コポリアミド。(1) It has a structural formula represented by the formula -(X-NH-Y-NH)-, in which X is the formula (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and Y is the formula ( B) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R is one selected from the group consisting of H, CH_3, C_2H_5.) and Formula (C) -CnH_2_n- (However, in the formula n is a positive number from 2 to 8), and a solution of 0.5 g of the copolyamide dissolved in 100 ml of dimethylacetamide was heated at 30°C
A soluble heat-resistant copolyamide having an intrinsic viscosity (ηinh) of 0.25 dl/g or more.
０：４０〜９９：１であり、前記測定法による固有粘度
（ηｉｎｈ）が０．３０ｄｌ／ｇである特許請求の範囲
第（１）項記載の可溶性耐熱コポリアミド。(2) The molar ratio of the chain member formula (B) and formula (C) of Y is 6
0:40 to 99:1, and has an intrinsic viscosity (ηinh) of 0.30 dl/g according to the measurement method.
ルフェノール、Ｎ−メチルピロリドン、及びジメチルア
セトアミドに溶解するものである特許請求の範囲第（１
）項記載の可溶性耐熱コポリアミド。(3) Claim No. 1 which is soluble in at least pyridine, m-cresol, o-chlorophenol, N-methylpyrrolidone, and dimethylacetamide.
) Soluble heat-resistant copolyamide described in section 2.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP87105719A EP0242818B1 (en) | 1986-04-22 | 1987-04-16 | Heat-resistant polyamide |
| DE8787105719T DE3780341D1 (en) | 1986-04-22 | 1987-04-16 | HEAT-RESISTANT POLYAMIDE. |
| US07/041,249 US4794159A (en) | 1986-04-22 | 1987-04-22 | Heat-resistant polyamide from bis(4-aminophenyl)fluorene |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13388186 | 1986-06-11 | ||
| JP61-133881 | 1986-06-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6399231A true JPS6399231A (en) | 1988-04-30 |
| JPH0331730B2 JPH0331730B2 (en) | 1991-05-08 |
Family
ID=15115266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4768887A Granted JPS6399231A (en) | 1986-04-22 | 1987-03-04 | Soluble and heat-resistant copolyamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6399231A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02193618A (en) * | 1989-01-20 | 1990-07-31 | Toray Ind Inc | Heat resistant container |
| JP2005015790A (en) * | 2003-06-06 | 2005-01-20 | Toray Ind Inc | Polymer having high refractive index and film having high refractive index obtained by using it |
| JP2020122097A (en) * | 2019-01-31 | 2020-08-13 | トヨタ紡織株式会社 | Polyamide compound |
-
1987
- 1987-03-04 JP JP4768887A patent/JPS6399231A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02193618A (en) * | 1989-01-20 | 1990-07-31 | Toray Ind Inc | Heat resistant container |
| JP2005015790A (en) * | 2003-06-06 | 2005-01-20 | Toray Ind Inc | Polymer having high refractive index and film having high refractive index obtained by using it |
| JP4539178B2 (en) * | 2003-06-06 | 2010-09-08 | 東レ株式会社 | Antireflection film, method for producing the same, and antireflection laminate |
| JP2020122097A (en) * | 2019-01-31 | 2020-08-13 | トヨタ紡織株式会社 | Polyamide compound |
| US11787905B2 (en) | 2019-01-31 | 2023-10-17 | Toyota Boshoku Kabushiki Kaisha | Polyamide compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0331730B2 (en) | 1991-05-08 |
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