JP2814517B2 - Aromatic diamine and aromatic polyamide - Google Patents
Aromatic diamine and aromatic polyamideInfo
- Publication number
- JP2814517B2 JP2814517B2 JP1042854A JP4285489A JP2814517B2 JP 2814517 B2 JP2814517 B2 JP 2814517B2 JP 1042854 A JP1042854 A JP 1042854A JP 4285489 A JP4285489 A JP 4285489A JP 2814517 B2 JP2814517 B2 JP 2814517B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- aromatic
- diamine
- solvent
- trimethylsilyl
- 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.)
- Expired - Lifetime
Links
- 239000004760 aramid Substances 0.000 title claims description 5
- 150000004984 aromatic diamines Chemical class 0.000 title claims description 5
- 229920003235 aromatic polyamide Polymers 0.000 title claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 description 25
- 229920002647 polyamide Polymers 0.000 description 25
- 239000002904 solvent Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 150000004985 diamines Chemical class 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000005855 radiation Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- RGFDKMDJAMMINO-UHFFFAOYSA-N 2-bromo-n,n-bis(trimethylsilyl)aniline Chemical compound C[Si](C)(C)N([Si](C)(C)C)C1=CC=CC=C1Br RGFDKMDJAMMINO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- SFAZXBAPWCPIER-UHFFFAOYSA-N chloro-[chloro(dimethyl)silyl]-dimethylsilane Chemical compound C[Si](C)(Cl)[Si](C)(C)Cl SFAZXBAPWCPIER-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- VIPCDVWYAADTGR-UHFFFAOYSA-N trimethyl(methylsilyl)silane Chemical compound C[SiH2][Si](C)(C)C VIPCDVWYAADTGR-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QDBOAKPEXMMQFO-UHFFFAOYSA-N 4-(4-carbonochloridoylphenyl)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=C(C(Cl)=O)C=C1 QDBOAKPEXMMQFO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- -1 aromatic diamine compound Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- NZZGQZMNFCTNAM-UHFFFAOYSA-N naphthalene-2,6-dicarbonyl chloride Chemical compound C1=C(C(Cl)=O)C=CC2=CC(C(=O)Cl)=CC=C21 NZZGQZMNFCTNAM-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- WKOUSCWUNLCUOG-UHFFFAOYSA-N 4-[[(4-aminophenyl)-dimethylsilyl]-dimethylsilyl]aniline Chemical compound C=1C=C(N)C=CC=1[Si](C)(C)[Si](C)(C)C1=CC=C(N)C=C1 WKOUSCWUNLCUOG-UHFFFAOYSA-N 0.000 description 1
- YJYMZGDBOMZWSR-UHFFFAOYSA-N 4-bromo-n,n-bis(trimethylsilyl)aniline Chemical compound C[Si](C)(C)N([Si](C)(C)C)C1=CC=C(Br)C=C1 YJYMZGDBOMZWSR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- JZALIDSFNICAQX-UHFFFAOYSA-N dichloro-methyl-trimethylsilylsilane Chemical compound C[Si](C)(C)[Si](C)(Cl)Cl JZALIDSFNICAQX-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical compound BrNC1=CC=CC=C1 ILCQYORZHHFLNL-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、新規な芳香族ジアミン化合物およびそれを
用いた芳香族ポリアミドに関する。Description: TECHNICAL FIELD The present invention relates to a novel aromatic diamine compound and an aromatic polyamide using the same.
［従来の技術］ 従来、集積回路などの製造においては、種々の感放射
線性材料が使用されている。しかし、近年製造工程の変
化などにより、高い耐熱性を有する感放射線性材料が必
要となってきているが、優れた耐熱性を有する感放射線
性材料は未だ得られていない。[Prior Art] Conventionally, various radiation-sensitive materials have been used in the manufacture of integrated circuits and the like. However, in recent years, radiation-sensitive materials having high heat resistance have been required due to changes in the manufacturing process and the like, but radiation-sensitive materials having excellent heat resistance have not yet been obtained.
［発明が解決しようとする問題点］ 本発明は、優れた耐熱性を有する感放射線性材料とし
て好適な芳香族ポリアミド、およびその芳香族ポリアミ
ドを製造するために使用される新規の芳香族ジアミンを
提供するものである。[Problems to be Solved by the Invention] The present invention relates to an aromatic polyamide suitable as a radiation-sensitive material having excellent heat resistance, and a novel aromatic diamine used for producing the aromatic polyamide. To provide.
［問題点を解決するための手段］ 本発明は、下記一般式（Ｉ）で表される芳香族ジアミ
ン（以下、「ジアミンＩ」という）を提供するものであ
る。[Means for Solving the Problems] The present invention provides an aromatic diamine represented by the following general formula (I) (hereinafter, referred to as “diamine I”).
また、本発明は、下記一般式（II） で表わされる繰り返し構造単位からなり、固有粘度（30
℃、Ｎ−メチルピロリドン中0.5g/dl）が0.01〜10dl/g
である芳香族ポリアミド（以下、「ポリアミドＩ」とい
う）を提供するものである。 Further, the present invention provides the following general formula (II): Consists of repeating structural units represented by
C, 0.5 g / dl in N-methylpyrrolidone) 0.01 to 10 dl / g
(Hereinafter referred to as “polyamide I”).
本発明においてジアミンＩは、例えば1,2−ジクロロ
テトラメチルジシランと〔ビス（トリメチルシリル）ア
ミノ〕フェニルリチウムとを反応させてN,N,N′,N′−
テトラ（トリメチルシリル）ジアミンを得た後、得られ
たN,N,N′,N′−テトラ（トリメチルシリル）ジアミン
と水とを反応させることによって製造することができ
る。In the present invention, the diamine I is, for example, N, N, N ', N'- by reacting 1,2-dichlorotetramethyldisilane with [bis (trimethylsilyl) amino] phenyllithium.
After obtaining tetra (trimethylsilyl) diamine, it can be produced by reacting the obtained N, N, N ', N'-tetra (trimethylsilyl) diamine with water.
ここで、〔ビス（トリメチルシリル）アミノ〕フェニ
ルリチウムは、例えば、ブロモアニリンを塩基の存在
下、クロロトリメチルシランと反応させて〔ビス（トリ
メチルシリル）アミノ〕ブロモベンゼンとし、さらにこ
の〔ビス（トリメチルシリル）アミノ〕ブロモベンゼン
にブチルリチウムを反応させることにより得ることがで
きる。Here, [bis (trimethylsilyl) amino] phenyllithium can be obtained, for example, by reacting bromoaniline with chlorotrimethylsilane in the presence of a base to give [bis (trimethylsilyl) amino] bromobenzene, and further adding the [bis (trimethylsilyl) amino] ] By reacting bromobenzene with butyllithium.
ジアミンＩの製法としては、具体的には〔ビス（トリ
メチルシリル）アミノ〕ブロモベンゼンとブチルリチウ
ムとを、モル比で、通常、1:1〜1:10、好ましくは1:3〜
1:5（〔ビス（トリメチルシリル）アミノ〕ブロモベン
ゼン：ブチルリチウム）の割合で反応させることにより
そのリチオ体とする。この反応の温度は、通常、−100
〜200℃であるが、−80〜80℃の温度で行なうことが好
ましい。この反応に使用しうる溶媒としては、実質的に
ブチルリチウムと反応しない溶媒が用いられ、特にエチ
ルエーテル、テトラヒドロフランなどのエーテル系溶媒
が好ましい。反応時間は、用いた試薬の量、溶媒の種
類、反応温度などに大きく左右されるが、数十分から数
日間反応させることが好ましい。As a method for producing diamine I, specifically, [bis (trimethylsilyl) amino] bromobenzene and butyllithium are usually used in a molar ratio of 1: 1 to 1:10, preferably 1: 3 to 1
Lithium is obtained by reacting at a ratio of 1: 5 ([bis (trimethylsilyl) amino] bromobenzene: butyllithium). The temperature of this reaction is usually -100
To 200 ° C, but preferably at a temperature of -80 to 80 ° C. As a solvent that can be used for this reaction, a solvent that does not substantially react with butyllithium is used, and an ether solvent such as ethyl ether or tetrahydrofuran is particularly preferable. The reaction time largely depends on the amount of the reagent used, the type of the solvent, the reaction temperature and the like, but it is preferable that the reaction is performed for several tens of minutes to several days.
次に、リチオ体を単離することなく、リチオ体と1,2
−ジクロロテトラメチルジシランとを、モル比で、通
常、2:1〜5:1（リチオ体:1,2−ジクロロテトラメチルジ
シラン）の割合で反応させてN,N,N′,N′−テトラ（ト
リメチルシリル）ジアミンとする。この反応の温度は、
通常、−100〜200℃であるが、−80〜80℃の温度で行な
うのが好ましい。この反応に使用しうる溶媒としては、
実質的にリチオ体や1,2−ジクロロテトラメチルジシラ
ンと反応しない溶媒が用いられ、特にエチルエーテル、
テトラヒドロフランなどのエーテル系溶媒が好ましい。
また、この反応ではクラウンエーテルなどのアニオン活
性化剤を共存させることもできる。反応時間は、用いた
試薬の量、溶媒の種類、反応温度などに大きく左右され
るが、数十分から数日間反応させることが好ましい。Next, without isolating the lithio form,
-Dichlorotetramethyldisilane is reacted with N, N, N ', N'- in a molar ratio, usually in a ratio of 2: 1 to 5: 1 (lithiated form: 1,2-dichlorotetramethyldisilane). Tetra (trimethylsilyl) diamine. The temperature of this reaction is
Usually, it is −100 to 200 ° C., but it is preferably performed at a temperature of −80 to 80 ° C. Solvents that can be used in this reaction include
A solvent that does not substantially react with the lithio compound or 1,2-dichlorotetramethyldisilane is used, and in particular, ethyl ether,
Ether solvents such as tetrahydrofuran are preferred.
In this reaction, an anionic activator such as a crown ether may be used. The reaction time largely depends on the amount of the reagent used, the type of the solvent, the reaction temperature and the like, but it is preferable that the reaction is performed for several tens of minutes to several days.
次いで、N,N,N′,N′−テトラ（トリメチルシリル）
ジアミンを水を用いて加水分解する。用いる水の量とし
ては、N,N,N′,N′−テトラ（トリメチルシリル）ジア
ミンに対し最低２倍モル必要であるが、他の溶媒と併用
してもよい。ここで用いる溶媒としては、メタノール、
エタノール、プロパノールなどのアルコール系溶媒、エ
チルエーテル、テトラヒドロフラン、ジオキサンなどの
エーテル系溶媒、ベンゼン、トルエンなどの芳香族系溶
媒、ジメチルホルムアミド、N,N−ジメチルアセトアミ
ドなどのアミド系溶媒、アセトンなどが例記できる。ま
た水と混合しない溶媒を使用するときには、四級アンモ
ニウム塩、クラウンエーテルなどの相間移動触媒を共存
させることもできる。反応時間は、用いた試薬の量、溶
媒の種類、反応温度などに大きく左右されるが、数十分
から数日間反応させることが好ましい。Then, N, N, N ', N'-tetra (trimethylsilyl)
The diamine is hydrolyzed with water. The amount of water used is at least twice as much as that of N, N, N ', N'-tetra (trimethylsilyl) diamine, but may be used in combination with another solvent. The solvent used here is methanol,
Examples include alcohol solvents such as ethanol and propanol, ether solvents such as ethyl ether, tetrahydrofuran and dioxane, aromatic solvents such as benzene and toluene, amide solvents such as dimethylformamide and N, N-dimethylacetamide, and acetone. Can be written. When a solvent that does not mix with water is used, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether can also be used. The reaction time largely depends on the amount of the reagent used, the type of the solvent, the reaction temperature and the like, but it is preferable that the reaction is performed for several tens of minutes to several days.
本発明のポリアミドＩを表わす一般式（II）におい
て、二価の芳香族基とは、以下に例示するジカルボン酸
ジハライドのハロゲン原子とカルボニル基を除いた基で
ある。また、本発明のポリアミンＩは、ジアミンＩとジ
カルボン酸ジハライドとを有機溶媒中で反応させること
により製造することができる。In the general formula (II) representing the polyamide I of the present invention, the divalent aromatic group is a group obtained by removing a halogen atom and a carbonyl group of a dicarboxylic acid dihalide exemplified below. The polyamine I of the present invention can be produced by reacting diamine I with dicarboxylic acid dihalide in an organic solvent.
ここで、ジカルボン酸ジハライドとしては、次のよう
な芳香族ジカルボン酸のジクロリド、ジフルオリド、ジ
ブロミドなどを例示することができる。芳香族ジカルボ
ン酸としては、テレフタル酸、2,6−ナフタレンジカル
ボン酸、4,4′−ビフェニルジカルボン酸、1,1,3−トリ
メチル−３−フェニルインダン−5,4′−ジカルボン酸
が挙げられる。Here, examples of the dicarboxylic acid dihalide include the following dichlorides of aromatic dicarboxylic acids, difluoride, dibromide and the like. Examples of the aromatic dicarboxylic acid include terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and 1,1,3-trimethyl-3-phenylindane-5,4'-dicarboxylic acid. .
これらのうちでは、4,4′−ビフェニルジカルボン酸
ジクロリド、2,6−ナフタレンジカルボン酸ジクロリ
ド、テレフタル酸ジクロリド、1,1,3−トリメチル−３
−フェニルインダン−5,4′−ジカルボン酸ジクロリド
などが好ましい。Among these, 4,4'-biphenyldicarboxylic acid dichloride, 2,6-naphthalenedicarboxylic acid dichloride, terephthalic acid dichloride, 1,1,3-trimethyl-3
-Phenylindane-5,4'-dicarboxylic acid dichloride and the like are preferred.
ポリアミドＩの製造は、具体的には、例えば有機溶媒
中、ジアミンＩと前記カルボン酸ジハライドとを、モル
比で通常1:0.5〜1:2、好ましくは1:0.8〜1:1.2（ジアミ
ンI:ジカルボン酸ジハライド）の割合で、−20〜200℃
で数分間から数日間反応させることにより行なわれる。For the production of polyamide I, specifically, for example, in an organic solvent, diamine I and the carboxylic acid dihalide are usually in a molar ratio of 1: 0.5 to 1: 2, preferably 1: 0.8 to 1: 1.2 (diamine I : Dicarboxylic acid dihalide) at -20 to 200 ° C
For several minutes to several days.
この方法に使用できる有機溶媒としては、N,N−ジメ
チルアセトアミド、Ｎ−メチル−２−ピロリドンなどの
アミド系溶媒、ベンゼン、アニソール、ジフェニルエー
テル、ニトロベンゼン、ベンゾニトリルなどの芳香族系
溶媒、クロロホルム、ジクロロメタン、1,2−ジクロロ
エタン、1,1,2,2−テトラクロロエタンなどのハロゲン
系溶媒などを例示することができる。このような有機溶
媒とともに、ピリジン、トリエチルアミンなどの酸受容
体を共存させて反応を行なうと効果的である。特に、N,
N−ジメチルアセトアミドやＮ−メチル−２−ピロリド
ンなどのアミド系溶媒を使用すると、これらの溶媒自身
が酸受容体となり高分子量のポリアミドＩを得ることが
できる。Organic solvents that can be used in this method include amide solvents such as N, N-dimethylacetamide and N-methyl-2-pyrrolidone, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene and benzonitrile, chloroform and dichloromethane. And 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, and the like. It is effective to carry out the reaction in the presence of such an organic solvent and an acid acceptor such as pyridine and triethylamine. In particular, N,
When an amide-based solvent such as N-dimethylacetamide or N-methyl-2-pyrrolidone is used, the solvent itself becomes an acid acceptor and high-molecular-weight polyamide I can be obtained.
本発明のポリアミドＩの固有粘度は、通常0.01〜10dl
/g、好ましくは0.05〜5dl/g（30℃、Ｎ−メチルピロリ
ドン中0.5g/dl）である。この固有粘度が0.01dl/g未満
であると、得られた成形品の機械的特性や耐熱性が不十
分となり、また、10dl/gを超えると有機溶媒への溶解性
が低下する。The inherent viscosity of the polyamide I of the present invention is usually 0.01 to 10 dl.
/ g, preferably 0.05 to 5 dl / g (30 ° C., 0.5 g / dl in N-methylpyrrolidone). If the intrinsic viscosity is less than 0.01 dl / g, the mechanical properties and heat resistance of the obtained molded product will be insufficient, and if it exceeds 10 dl / g, the solubility in organic solvents will decrease.
ポリアミドＩは、使用したジカルボン酸ジハライドの
種類によりその溶解性が変化するが、N,N′−ジメチル
ホルムアミド、N,N−ジメチルアセトアミド、ジメチル
スルホキシド、ピリジンなどの溶媒のすべてに、または
一部に可溶となる。また、ポリアミドＩは、紫外線、Ｘ
線などの放射線の照射により分子量の低下が認められ
る。さらに、本発明のポリアミドＩは200〜250℃付近の
高いガラス転移点を有し、350〜400℃付近まで加熱して
も顕著な重量変化は認められない。Polyamide I varies in solubility depending on the type of dicarboxylic acid dihalide used, but may be used in all or a part of solvents such as N, N'-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and pyridine. It becomes soluble. In addition, polyamide I is an ultraviolet ray, X
Irradiation with radiation such as radiation reduces the molecular weight. Furthermore, the polyamide I of the present invention has a high glass transition temperature of around 200 to 250 ° C, and no remarkable weight change is observed even when heated to around 350 to 400 ° C.
［実 施 例］ 以下、本発明を実施例によりさらに詳細に説明する。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
実 施 例 ｐ−〔ビス（トリメチルシリル）アミノ〕ブロモベン
ゼン21.356g（67.5mmol）を、150mlのエチルエーテルに
溶解した溶液に窒素気流下、−10℃で42.2ml（67.5mmo
l）のブチルリチウム溶液（1.6モル濃度のヘキサン溶
液）を滴下した。滴下終了後、０℃で２時間攪拌したと
ころ、４−〔ビス（トリメチルシリル）アミノフェニル
リチウムの溶液が得られた。引き続き、この溶液に1,2
−ジクロロテトラメチルジシラン6.311g（33.75mmol）
を０℃で滴下し、０℃で２時間、25℃で12時間、加熱還
流下で１時間攪拌した。生成した白色沈殿を分離後、液
層を蒸留精製し、156℃/0.1Torrの留分を捕集した。得
られた化合物は、赤外吸収スペクトルデータから1,2−
ビス〔４−N,N−ジ（トリメチルシリル）アミノフェニ
ル〕テトラメチルジシラン（以下、「化合物Ｉ」とい
う）であると同定された。EXAMPLES Example 1 A solution of 21.356 g (67.5 mmol) of p- [bis (trimethylsilyl) amino] bromobenzene in 150 ml of ethyl ether was added with 42.2 ml (67.5 mmol) at −10 ° C. under a nitrogen stream.
l) A butyllithium solution (1.6 molar hexane solution) was added dropwise. After completion of the dropwise addition, the mixture was stirred at 0 ° C for 2 hours to obtain a solution of 4- [bis (trimethylsilyl) aminophenyllithium. Then add 1,2
-6.311 g (33.75 mmol) of dichlorotetramethyldisilane
Was added dropwise at 0 ° C., and the mixture was stirred at 0 ° C. for 2 hours, at 25 ° C. for 12 hours, and under heating and refluxing for 1 hour. After separating the generated white precipitate, the liquid layer was purified by distillation, and a fraction at 156 ° C./0.1 Torr was collected. The obtained compound was identified as 1,2-
It was identified as bis [4-N, N-di (trimethylsilyl) aminophenyl] tetramethyldisilane (hereinafter, referred to as "compound I").
次に、化合物I20gを10重量％の水を含むアセトン200m
l中に溶解し、溶媒を減圧留去することで加水分解し、
下記式で表わされる1,2−ビス（４−アミノフェニル）
テトラメチルジシランを得た。このものを、さらにヘキ
サンより再結晶することにより精製した。Next, 200 g of acetone containing 10% by weight of water was added to 20 g of Compound I.
dissolved in l, hydrolyzed by distilling off the solvent under reduced pressure,
1,2-bis (4-aminophenyl) represented by the following formula
Tetramethyldisilane was obtained. This was further purified by recrystallization from hexane.
以下に、得られた1,2−ビス（４−アミノフェニル）
テトラメチルジシランの性質を示す。Hereinafter, the obtained 1,2-bis (4-aminophenyl)
Shows the properties of tetramethyldisilane.
融点:108〜110℃ 赤外吸収スペクトル： 第１図に示す。Melting point: 108-110 ° C Infrared absorption spectrum: shown in FIG.
H1−NMR（CDCl3）［δ、ppm］： 0.25（12H）、3.50（4H）、6.75ppm（8H） UVスペクトル:300 262nm（テトラヒドロフラン中） （εmax＝23254） 分子量:300 元素分析値 Ｃ Ｈ Ｎ 計算値（％） 63.94 8.05 9.32 実測値（％） 64.24 8.66 8.87 実施例２ 1,2−ビス（４−アミノフェニル）テトラメチルジシ
ラン0.301g（1.0mmol）を5mlのＮ−メチル−２−ピロリ
ドンに溶解し、ドライアイス−アセトン浴で凍結した。
これに0.203g（1.0mmol）のテレフタル酸ジクロリドを
固体のまま一度に加えた。ドライアイス−アセトン浴か
ら氷浴にかえ、０℃で３時間攪拌後、得られた粘稠な溶
液を300mlの蒸留水中に投入することにより、下記の構
造単位を有するポリアミドを得た。H 1 -NMR (CDCl 3 ) [δ, ppm]: 0.25 (12H), 3.50 (4H), 6.75 ppm (8H) UV spectrum: 300 262 nm (in tetrahydrofuran) (ε max = 23254) Molecular weight: 300 Elemental analysis value Calculated value of CHN (%) 63.94 8.05 9.32 Actual value (%) 64.24 8.66 8.87 Example 2 0.301 g (1.0 mmol) of 1,2-bis (4-aminophenyl) tetramethyldisilane was dissolved in 5 ml of N-methyl-2-pyrrolidone and frozen in a dry ice-acetone bath.
To this, 0.203 g (1.0 mmol) of terephthalic acid dichloride was added all at once as a solid. After changing from a dry ice-acetone bath to an ice bath and stirring at 0 ° C. for 3 hours, the resulting viscous solution was poured into 300 ml of distilled water to obtain a polyamide having the following structural unit.
得られたポリアミドの赤外吸収スペクトルを測定した
結果を第２図に示す。FIG. 2 shows the result of measuring the infrared absorption spectrum of the obtained polyamide.
また、得られたポリアミドの固有粘度、元素分析結
果、ガラス転移温度および10％重量減少温度を第１表に
示す。Table 1 shows the intrinsic viscosity, the results of elemental analysis, the glass transition temperature, and the 10% weight loss temperature of the obtained polyamide.
実施例３ テレフタル酸ジクロリドの代わりに、2,6−ナフタレ
ンジカルボン酸ジクロリド0.253g（1.0mmol）を用いた
以外は実施例２と同様にして、下記の構造単位を有する
ポリアミドを得た。 Example 3 A polyamide having the following structural unit was obtained in the same manner as in Example 2 except that 0.253 g (1.0 mmol) of 2,6-naphthalenedicarboxylic acid dichloride was used instead of terephthalic acid dichloride.
また、得られたポリアミドの固有粘度、元素分析結
果、ガラス転移温度および10％重量減少温度を第１表に
示す。Table 1 shows the intrinsic viscosity, the results of elemental analysis, the glass transition temperature, and the 10% weight loss temperature of the obtained polyamide.
実施例４ テレフタル酸ジクロリドの代わりに、4,4′−ビフェ
ニルジカルボン酸ジクロリド0.279g（1.0mmol）を用い
た以外は実施例２と同様にして、下記の構造単位を有す
るポリアミドを得た。 Example 4 A polyamide having the following structural unit was obtained in the same manner as in Example 2 except that 0.279 g (1.0 mmol) of 4,4'-biphenyldicarboxylic acid dichloride was used instead of terephthalic acid dichloride.
得られたポリアミドの赤外吸収スペクトルを測定し
た。結果を第３図に示す。The infrared absorption spectrum of the obtained polyamide was measured. The results are shown in FIG.
また、得られたポリアミドの固有粘度、元素分析結
果、ガラス転移温度および10％重量減少温度を第１表に
示す。Table 1 shows the intrinsic viscosity, the results of elemental analysis, the glass transition temperature, and the 10% weight loss temperature of the obtained polyamide.
実施例５ テレフタル酸ジクロリドの代わりに、1,1,3−トリメ
チル−３−フェニルインダン−5,4′−ジカルボン酸ジ
クロリド0.361g（1.0mmol）を用いた以外は実施例２と
同様にして、下記の構造単位を有するポリアミドを得
た。 Example 5 The procedure of Example 2 was repeated, except that 0.361 g (1.0 mmol) of 1,1,3-trimethyl-3-phenylindane-5,4'-dicarboxylic acid dichloride was used instead of terephthalic acid dichloride. A polyamide having the following structural unit was obtained.
得られたポリアミドの赤外吸収スペクトルを測定し
た。結果を第４図に示す。The infrared absorption spectrum of the obtained polyamide was measured. The results are shown in FIG.
また、得られたポリアミドの固有粘度、元素分析結
果、ガラス転移温度および10％重量減少温度を第１表に
示す。Table 1 shows the intrinsic viscosity, the results of elemental analysis, the glass transition temperature, and the 10% weight loss temperature of the obtained polyamide.
試験例１ 実施例２〜５で得られたポリアミドを1gを第２表に示
す各溶媒100mlに入れ、25℃で溶解性を調べた。結果を
第２表に示す。 Test Example 1 1 g of the polyamide obtained in Examples 2 to 5 was placed in 100 ml of each solvent shown in Table 2, and the solubility was examined at 25 ° C. The results are shown in Table 2.
試験例２ 実施例５で得られたポリアミドの５重量％N,N−ジメ
チルアセトアミド溶液に、400W高圧水銀灯を用いて、紫
外線を照射したときの紫外線照射時間と、ポリアミド溶
液の固有粘度との関係を測定した。結果を第５図に示
す。Test Example 2 Relationship between UV irradiation time when UV light was irradiated to a 5% by weight N, N-dimethylacetamide solution of the polyamide obtained in Example 5 using a 400 W high-pressure mercury lamp, and the intrinsic viscosity of the polyamide solution. Was measured. The results are shown in FIG.
［発明の効果］ 本発明の芳香族ジアミンは、ポリアミドの原料として
有用であり、得られるポリアミドは優れた耐熱性を有
し、しかも放射線感応性であるので、例えばポジ型レジ
ストとして好適である。 [Effects of the Invention] The aromatic diamine of the present invention is useful as a raw material for polyamide, and the resulting polyamide has excellent heat resistance and is radiation-sensitive, and thus is suitable as, for example, a positive resist.
第１図〜第４図は、実施例１、２、４および５で得られ
た化合物または重合体の赤外吸収スペクトルの結果を示
す図であり、第５図は、試験例２における紫外線照射時
間とポリアミド溶液の固有粘度との関係を示す図であ
る。1 to 4 are views showing the results of infrared absorption spectra of the compounds or polymers obtained in Examples 1, 2, 4 and 5, and FIG. It is a figure which shows the relationship between time and the intrinsic viscosity of a polyamide solution.
Claims (2)
ン。 1. An aromatic diamine represented by the following general formula (I).
℃、Ｎ−メチルピロリドン中0.5g/dl）が0.01〜10dl/g
である芳香族ポリアミド。2. The following general formula (II) Consists of repeating structural units represented by
C, 0.5 g / dl in N-methylpyrrolidone) 0.01 to 10 dl / g
Is an aromatic polyamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1042854A JP2814517B2 (en) | 1989-02-22 | 1989-02-22 | Aromatic diamine and aromatic polyamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1042854A JP2814517B2 (en) | 1989-02-22 | 1989-02-22 | Aromatic diamine and aromatic polyamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02219825A JPH02219825A (en) | 1990-09-03 |
| JP2814517B2 true JP2814517B2 (en) | 1998-10-22 |
Family
ID=12647605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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| JP2010163405A (en) * | 2009-01-19 | 2010-07-29 | Univ Of Tokyo | Arylated product of hydrooligosilane, luminescence material or electron-transport material containing the same and method for producing the arylated product of hydrooligosilane |
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1989
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| JPH02219825A (en) | 1990-09-03 |
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