JPS6341456A - Novel bismaleimide compound and production thereof - Google Patents
Novel bismaleimide compound and production thereofInfo
- Publication number
- JPS6341456A JPS6341456A JP18431286A JP18431286A JPS6341456A JP S6341456 A JPS6341456 A JP S6341456A JP 18431286 A JP18431286 A JP 18431286A JP 18431286 A JP18431286 A JP 18431286A JP S6341456 A JPS6341456 A JP S6341456A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- reaction
- compound shown
- bismaleimide compound
- solvent
- 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
- -1 bismaleimide compound Chemical class 0.000 title claims abstract description 18
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 229920001721 polyimide Polymers 0.000 abstract description 7
- 239000009719 polyimide resin Substances 0.000 abstract description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 6
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 229920006122 polyamide resin Polymers 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 150000004985 diamines Chemical class 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000140 heteropolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は新規なビスマレイミド化合物に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to novel bismaleimide compounds.
（従来技術及び問題点）
Ｎ−Ｎ’−（メチレン−ジーｐ−）二二しン）ビスマレ
イミドの様な化合物は、特にポリイミド樹脂原料として
従来から知られている。(Prior Art and Problems) Compounds such as N-N'-(methylene-p-)dinidine)bismaleimide have been known for a long time, especially as raw materials for polyimide resins.
黙しながらこの様なビスマレイミド化合物を用いてポリ
イミド樹脂を形成した場合、該ポリマー構造中を占める
官能基結合部分の割合が大きいために、該樹脂は固く締
ったものとなり、硬いが脆いという欠点を有している。However, when a polyimide resin is formed using such a bismaleimide compound, the resin becomes hard and compact due to the large proportion of the functional group bonding moiety in the polymer structure, which has the disadvantage of being hard but brittle. have.
従って；４．、発明は、ポリイミド樹脂の有する耐熱性
を損なうことなく適度な柔軟性を与え１強靭性を有する
ポリイミド樹脂を得ることが可能な新規ビスマレイミド
化合物を提供することを技術的課届とする。Therefore; 4. The technical purpose of the present invention is to provide a new bismaleimide compound that can provide a polyimide resin with appropriate flexibility and toughness without impairing the heat resistance of the polyimide resin.
（発明の構成）
未発ｌｙＩのビスマレイミド化合物は、Ｆ記−数式、
・・・・ ・・（１１
式中、Ｒ１乃至ＲＡ及びＲ、ｉ乃至Ｒａ’は、水、ぐ原
Ｐ、ハロゲン原子、或いは炭素数１乃至４のアルキルノ
、（を示す、
で表わされる。(Structure of the Invention) The undeveloped lyI bismaleimide compound has the following formula: (11) In the formula, R1 to RA and R, i to Ra' are water, P, and a halogen atom. , or alkylno having 1 to 4 carbon atoms.
（作 用）
このビスマレイミド化合物は、分子骨格が非対称的であ
るという特徴を有している。(Function) This bismaleimide compound is characterized by an asymmetric molecular skeleton.
即ち、かような非対称的構造を有するビスマレイミド化
合物を用いてポリイミド樹脂を構成した場合には、出該
樹脂の構成分子は規則正しい結晶構造を構成しないため
、適度な柔軟性が付与され、その脆さが４片するのであ
る。In other words, when a polyimide resin is constructed using a bismaleimide compound having such an asymmetric structure, the constituent molecules of the resin do not constitute a regular crystal structure, which imparts appropriate flexibility and reduces its brittleness. There are four pieces.
（発明の好適実施態様）
本発明のビスマレイミド化合物は、丁記一般式、
１（ｌ′
・・・ ・・・・・（′！１
式中、Ｒ１乃至Ｒ４及びＲ１′乃至１’＋４’は、水素
原子、ハロゲン原子、或いは炭素数１乃至４のアルキル
基を示す、
で表わされるジアミンと無水マレイン酸との脱水縮合反
応により得られる。(Preferred Embodiment of the Invention) The bismaleimide compound of the present invention has the following general formula: 1(l'......('!1) In the formula, R1 to R4 and R1' to 1'+4' is obtained by a dehydration condensation reaction between a diamine represented by the following formula, which represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and maleic anhydride.
」二記の一般式（２）で表わされるジアミンとしては、
具体的には、２．２−（３−アミノフェニル）−（４−
アミ／フェニル）プロパン或いはそのハロゲン乃至はア
ルキル置換体が使用される。” As the diamine represented by the general formula (2),
Specifically, 2.2-(3-aminophenyl)-(4-
Ami/phenyl)propane or its halogen or alkyl substituted product is used.
脱水縮合反応は、例えばＬ記のジアミン、無水マレイン
酸及び酸性触媒を所定の后奴中に溶解乃至分散させて、
加／８還流することにより行なわれる。The dehydration condensation reaction can be carried out, for example, by dissolving or dispersing the diamine of L, maleic anhydride, and an acidic catalyst in a predetermined solution.
This is done by adding/8 reflux.
酸性触媒としては、硫酸、塩酸、リン酸等の鉱酸、リン
タングステン酸、リンモリブデン酸等のへテロポリ酎、
Ｐ−トルエンスルホン酸、メタンスルホン酸等の有機ス
ルホン酸、トリクロル酢酸、トリフルオル酢酸等のノ＼
ロゲン化カルボン酸、シリカアルミナ等の固体酸、カチ
オン交換型イオン交換樹脂等が使用され、特に硫酸、リ
ン酸、Ｐｌルエンスルホン酸が好適である。またこれら
の酸は、ジアミンとの塩の形となって１７）でもよい。Examples of acidic catalysts include mineral acids such as sulfuric acid, hydrochloric acid, and phosphoric acid; heteropolymer acids such as phosphotungstic acid and phosphomolybdic acid;
Organic sulfonic acids such as P-toluenesulfonic acid and methanesulfonic acid, trichloroacetic acid, trifluoroacetic acid, etc.
A halogenated carboxylic acid, a solid acid such as silica alumina, a cation exchange type ion exchange resin, etc. are used, and sulfuric acid, phosphoric acid, and Pl luenesulfonic acid are particularly preferred. These acids may also be in the form of salts with diamines (17).
これらの酸性触媒は、その種類によっても異なるが、一
般に無水マレイン酸と前記ジアミンとの合計量当たり０
．５乃至５重量％の量で使用することが望ましい。Although these acidic catalysts vary depending on their type, they generally contain 0% per total amount of maleic anhydride and the diamine.
．． Preferably, it is used in an amount of 5 to 5% by weight.
触媒贋が０．５重量％よりも少ない場合には所望の触媒
効果が達成されず、また５取量％より多く用いたとして
も一定以北の効果が得られず、経済的に不利となるばか
りか、残存触媒の除去が困難となる。If the catalyst content is less than 0.5% by weight, the desired catalytic effect will not be achieved, and even if more than 5% is used, no effect beyond a certain level will be obtained, which is economically disadvantageous. Moreover, it becomes difficult to remove the remaining catalyst.
縮合反応に際して用いる溶媒としては、ヘキサン、ヘプ
タン、デカン、シクロヘキサン等の脂肪族乃至脂環族炭
化水素、ベンゼン、トルエン、キシレン等の芳香）Ｓｉ
Ｒ化水素、これら脂肪族又は芳香族炭化水素のハロゲン
化物、ジメチルホルムアミド、Ｎ−メチルピロリドン、
アセトニトリル、ジメチルアセトアミド゛、ジメチルス
ルホキシド。Solvents used in the condensation reaction include aliphatic or alicyclic hydrocarbons such as hexane, heptane, decane, and cyclohexane, aromatic compounds such as benzene, toluene, and xylene).
R-hydrogen, halides of these aliphatic or aromatic hydrocarbons, dimethylformamide, N-methylpyrrolidone,
Acetonitrile, dimethylacetamide, dimethyl sulfoxide.
スルホラン、アニソール、ｎ−ブチルエーテル笠の含酸
素、含窒素又は含硫黄極性溶媒、及びこれらの混合溶媒
が使用される。Oxygen-containing, nitrogen-containing or sulfur-containing polar solvents such as sulfolane, anisole, n-butyl ether, and mixed solvents thereof are used.
溶媒量は、一般に前記ジアミン成分及び無水マレイン酸
との合計量の１乃至２０倍、特に３乃至１０倍の範囲に
あることが好適である。The amount of solvent is generally 1 to 20 times, particularly preferably 3 to 10 times, the total amount of the diamine component and maleic anhydride.
加熱還流下における反応温度は、用いる溶媒等によって
も若干異なるが、一般に８０乃至１９０℃、特に１２０
℃乃至１６０℃の範囲が好適である。圧力は加圧、常圧
、減圧の何れでもよく、用いる溶媒と反応温度とに応じ
て適宜選択される。The reaction temperature under heating under reflux varies slightly depending on the solvent used, but is generally 80 to 190°C, particularly 120°C.
A range of 160°C to 160°C is preferred. The pressure may be increased pressure, normal pressure, or reduced pressure, and is appropriately selected depending on the solvent used and the reaction temperature.
反応時間は一般に２乃至１０時間、特に５乃至６時間の
範囲にある。The reaction time is generally in the range from 2 to 10 hours, especially from 5 to 6 hours.
尚、無水マレイン酸とジアミン成分の仕込み量は、ジア
ミン成分に対して無水マレイン酸量を若干過剰とするこ
とが好適である。一般には、モル基準で、無水マレイン
酸／ジアミン成分＝ ２．０５乃至３．０とする様に仕
込めばよい。It is preferable that the amounts of maleic anhydride and diamine component to be charged are such that the amount of maleic anhydride is slightly in excess of the diamine component. In general, the maleic anhydride/diamine component may be charged at a ratio of 2.05 to 3.0 on a molar basis.
縮合反応完了後１反応混合物を水洗して、残存触媒、未
反応無水マレイン酸を除去した後、溶媒を留去して濃縮
物を得る。この濃縮物にアルコールを加えて攪拌すると
、結晶粉末が得られる。得られた粗結晶をアルコール溶
媒によって再結晶精製する。After completion of the condensation reaction, the reaction mixture is washed with water to remove residual catalyst and unreacted maleic anhydride, and then the solvent is distilled off to obtain a concentrate. When alcohol is added to this concentrate and stirred, a crystalline powder is obtained. The obtained crude crystals are purified by recrystallization using an alcohol solvent.
この再結晶品を、赤外吸収ズベクトル、核磁気共鳴スペ
クトル、質量分析及び元素分析により同定することによ
り、前記−数式（１）で表わされるビスマレイミド化合
物であることが確認された。This recrystallized product was identified by infrared absorption Zvector, nuclear magnetic resonance spectrum, mass spectrometry, and elemental analysis, and was confirmed to be a bismaleimide compound represented by formula (1) above.
以下に本発明のビスマレイミド化合物の物性等を示す。The physical properties of the bismaleimide compound of the present invention are shown below.
Ｎ、Ｎ’−（２，２−プロピリデン−（ｍ−フェニレン
）−（ｐ−）二二しン））ビスマレイミド
結晶形態：淡黄色粉末
融 点：１３７乃至１３８℃
（用 途）
本発明の新規ビスマレイミド化合物は、分子骨格が非対
称的な構造を有しており、強靭性を有するポリイミド樹
脂用原料として極めて有用である。N,N'-(2,2-propylidene-(m-phenylene)-(p-)dinidine))bismaleimide Crystal form: Pale yellow powder Melting point: 137 to 138°C (Applications) The present invention The new bismaleimide compound has an asymmetric molecular skeleton structure and is extremely useful as a raw material for polyimide resin having toughness.
（実施例）
実施例 ｌ
温度計鞘、還流冷却器、滴下か斗、及び攪拌器を備えた
１ｆ４０フラスコに、無水マレイン酸２０．８ｇ （０
，２１モル）、Ｐ−トルエンスルホン酸ｌ永和物１．５
８ｇ （０，００８モル）を混合キシレン３００ｒｘｌ
とともに仕込んだ。Examples Example 1 Into a 1f40 flask equipped with a thermometer sheath, reflux condenser, addition funnel, and stirrer, 20.8 g of maleic anhydride (0
, 21 mol), P-toluenesulfonic acid 1.5
8g (0,008mol) mixed xylene 300rxl
I prepared it with
このフラスコを油浴に浸し、フラスコ内容物を１４０℃
まで昇温せしめた。Immerse this flask in an oil bath and heat the flask contents to 140°C.
The temperature was raised to .
一方、滴下か斗の中に、２．２−（３−７ミノフエニル
）−（４−７ミノフエニル）プロパノン２２．８ｇ （
０，１モル）を混合キシレン１５０ｍｆとＮ、Ｎ−ジメ
チルホルムアミド３５ｍ＋／ｉとを混合した混合溶媒に
溶かした溶液を調製した。Meanwhile, in a dropping funnel, add 22.8 g of 2.2-(3-7minophenyl)-(4-7minophenyl)propanone (
A solution was prepared by dissolving 0.1 mol) in a mixed solvent of 150 mf of mixed xylene and 35 m+/i of N,N-dimethylformamide.
フラスコ内温度が所定の温度に達し、混合キシレノの還
流が始まったところで滴下ｒ外内の前記溶液の滴下を開
始した。When the temperature inside the flask reached a predetermined temperature and reflux of the mixed xylene began, dropping of the solution inside the flask was started.
滴下ｐ耳内溶液の全量を５時間かけて滴下し、滴下終了
後、更に後反応を１時間行なった。The entire amount of the intraaural solution was dropped over a period of 5 hours, and after the drop was completed, a post-reaction was further carried out for 1 hour.
上記反応において、２．２（３−７ミノフエニル）−（
４−７ミノフエニル）プロパンの滴下を開始すると同時
に、反応生成水とキシレンの共沸が始まった。In the above reaction, 2.2(3-7minophenyl)-(
At the same time as starting the dropwise addition of 4-7minophenyl)propane, azeotropy of reaction product water and xylene began.
反応生成水は、還流冷却器と反応フラスコの間に取り付
けた水抜き取り器に全量集めた。The entire amount of reaction product water was collected in a water drainer installed between the reflux condenser and the reaction flask.
反応終了後、フラスコ内の反応混合物をロータリーエバ
ポレータに移し、８０℃、１２５ｍコＨｇの条件下でｅ
縮を行ない、濃縮物７４．８ｇを得た。After the reaction was completed, the reaction mixture in the flask was transferred to a rotary evaporator and evaporated at 80°C and 125 mHg.
Condensation was performed to obtain 74.8 g of concentrate.
この濃縮物全量をエタノール５００＋ｊ！の中に投入し
、加熱しながら混合物の攪拌を行ない、反応生成物を固
形化させた。The entire amount of this concentrate is ethanol 500+j! and stirred the mixture while heating to solidify the reaction product.
次いでこの生成物のスラリーを冷却後、東上小型遠心分
離機を用いて固−液分離を行なった。After cooling the product slurry, solid-liquid separation was performed using a small Tojo centrifuge.
分離された固形物を減圧下に屹爆し、結晶３３．０ｇを
得た。該結晶の一部を取ってエタノール溶媒により再結
晶を行なった。The separated solid was exploded under reduced pressure to obtain 33.0 g of crystals. A portion of the crystals was taken and recrystallized using ethanol solvent.
この再結晶品の融点は、１３７乃至１３８°Ｃであった
。The melting point of this recrystallized product was 137 to 138°C.
この再結晶品について、赤外吸収スペクトル、核磁気共
鳴吸収スペクトル、質量スペクトルを測定した。各スペ
クトルをそれぞれ７ｆＳｔ図乃至第３図に示す。Infrared absorption spectrum, nuclear magnetic resonance absorption spectrum, and mass spectrum were measured for this recrystallized product. Each spectrum is shown in the 7fSt diagram to FIG. 3, respectively.
第１図の赤外吸収スペクトルから明らかな通り、カルボ
ニル基（〉Ｃ＝○）の存在（１７１０ｃｍ−ｌの吸収ピ
ーク）及びイミド３（−Ｎ＜）の存在（１７７５ｃ＋ｏ
−１の吸収ピーク）が明らかである。As is clear from the infrared absorption spectrum in Figure 1, the presence of carbonyl group (〉C=○) (absorption peak at 1710 cm-l) and the presence of imide 3 (-N<) (1775c+o
-1 absorption peak) is clear.
また第２図の核磁気共鳴吸収スペクトルの結果から、１
．７０ｐｐｍ 、 ８．９１ｐｐｍ及び？、２８ｐＰ
■、のピークまた、第３図の質量スペクトルより、ｍ／
ｅ＝３８６の位置に親ピークが認められる。Also, from the results of the nuclear magnetic resonance absorption spectrum shown in Figure 2, 1
．． 70ppm, 8.91ppm and ? , 28pP
■The peak of m/
A parent peak is observed at the position e=386.
更に、この結晶体について元素分析を行なった結果１次
の通りであった。Furthermore, elemental analysis was performed on this crystal, and the results were as follows.
ＣＨＮ
分析イ直 （％） ？＋、２５ ４，
８２ ７．２５（計算値） ／／ ７１．
４９ ４．７０ ７．２５以上の結果から、上記結
晶は、下記式、で表わされるＮ、Ｎ′−（２，２−プロ
ピリデン−（ｍ−フェニレン）−（Ｐ−フェニレン））
ビスマレイミドであるものと認められる。CHN Direct analysis (%)? +, 25 4,
82 7.25 (calculated value) // 71.
49 4.70 7.25 From the above results, the above crystal has N,N'-(2,2-propylidene-(m-phenylene)-(P-phenylene)) represented by the following formula.
It is recognized to be bismaleimide.
第１図、第２図及び第３図は、実施例１の合成物の赤外
吸収スペクトル、核ｒｉｉ気共鳴スペクトル、ｆｉｆｆ
ｉスペクトルをそれぞれ示す。1, 2, and 3 show the infrared absorption spectrum, nuclear rii gas resonance spectrum, and fiff of the composite of Example 1.
i spectra are shown respectively.
Claims (2)
、水素原子、ハロゲン原子或いは炭素数１乃 至４のアルキル基を示す。） で表わされることを特徴とするビスマレイミド化合物。(1) The following general formula, ▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R_1 to R_4 and R_1' to R_4' represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.) A bismaleimide compound represented by:
水素原子、ハロゲン原子或いは炭素 原子１乃至４のアルキル基を表わす で表わされるジアミン化合物と無水マレイン酸を、酸性
触媒の存在下に、脂肪族炭化水素、脂環族炭化水素、芳
香族炭化水素、これら脂肪族又は芳香族炭化水素のハロ
ゲン化物、含酸素、含窒素又は含硫黄極性溶媒を溶媒と
し、あるいはこれらの混合物を溶媒として加熱還流下に
、反応で生成する水を系外に除去しながら反応を行うこ
とを特徴とする 新規ビスマレイミド化合物の製造方法。(2) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1 to R_4 and R_1' to R_4' are
A diamine compound represented by a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms, and maleic anhydride are mixed in the presence of an acidic catalyst with an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, Using a halide, oxygen-containing, nitrogen-containing or sulfur-containing polar solvent of these aliphatic or aromatic hydrocarbons as a solvent, or a mixture thereof, the reaction is heated under reflux while removing water produced by the reaction from the system. A method for producing a novel bismaleimide compound, which comprises carrying out a reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18431286A JPH0686425B2 (en) | 1986-08-07 | 1986-08-07 | Novel bismaleimide compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18431286A JPH0686425B2 (en) | 1986-08-07 | 1986-08-07 | Novel bismaleimide compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6341456A true JPS6341456A (en) | 1988-02-22 |
| JPH0686425B2 JPH0686425B2 (en) | 1994-11-02 |
Family
ID=16151134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18431286A Expired - Fee Related JPH0686425B2 (en) | 1986-08-07 | 1986-08-07 | Novel bismaleimide compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0686425B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993012933A1 (en) * | 1991-12-27 | 1993-07-08 | Sumitomo Chemical Company, Limited | Polyamino-oligomer and polymaleimide compound |
| US6777526B2 (en) * | 2001-08-24 | 2004-08-17 | Tosoh Corporation | Optically active maleimide derivatives, optically active polymaleimide derivatives, production method thereof, separating agent using the same derivative, and method for separating optically active compounds using the same agent |
| JP2008008992A (en) * | 2006-06-27 | 2008-01-17 | Nippon Telegr & Teleph Corp <Ntt> | Method and tool for cleaning end face of optical fiber |
-
1986
- 1986-08-07 JP JP18431286A patent/JPH0686425B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993012933A1 (en) * | 1991-12-27 | 1993-07-08 | Sumitomo Chemical Company, Limited | Polyamino-oligomer and polymaleimide compound |
| US5399715A (en) * | 1991-12-27 | 1995-03-21 | Sumitomo Chemical Company, Limited | Polyamino oligomers and polymaleimide compounds |
| US6777526B2 (en) * | 2001-08-24 | 2004-08-17 | Tosoh Corporation | Optically active maleimide derivatives, optically active polymaleimide derivatives, production method thereof, separating agent using the same derivative, and method for separating optically active compounds using the same agent |
| JP2008008992A (en) * | 2006-06-27 | 2008-01-17 | Nippon Telegr & Teleph Corp <Ntt> | Method and tool for cleaning end face of optical fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0686425B2 (en) | 1994-11-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH03275669A (en) | New bisphenols containing imide ring and production thereof | |
| US4758380A (en) | Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis | |
| JPS6341456A (en) | Novel bismaleimide compound and production thereof | |
| JPS58180479A (en) | Manufacture of aromatic bis(ether acid anhydride) | |
| WO2006085493A1 (en) | Aromatic diamine and process for producing the same | |
| JPS6335561A (en) | Novel bismaleimide compound and production thereof | |
| JP3433482B2 (en) | Method for producing bismaleimide | |
| JPH04364147A (en) | 1,3-dihydroxy-4,6-bis(alpha-methyl-alpha-(4'-hydroxyphenyl) ethyl)benzene and its production | |
| JP2628374B2 (en) | Bismaleimide compound and method for producing the same | |
| JPH06116191A (en) | Production of 1,3-dihydroxy-4,6-bis(alpha-methyl-alpha-@(3754/24)4'-hydroxyphenyl)ethyl)benzene | |
| JP2531724B2 (en) | Biscitraconimide compound and method for producing the same | |
| JPH0539346A (en) | Polymaleimide compound | |
| JPH0446155A (en) | 4-(hydroxyphenoxy)phenylmaleimide and production thereof | |
| KR940006437B1 (en) | Bismaleimide compound and method for their preparation | |
| JP3085610B2 (en) | Method for producing bismaleimides | |
| JPS63201166A (en) | Novel maleimide compound and production thereof | |
| JP3085609B2 (en) | Method for producing bismaleimides | |
| JP3132784B2 (en) | Method for producing 3,3'-dinitro-5,5'-bis (trifluoromethyl) diphenyl ether | |
| JPH06107629A (en) | Method for purifying bismaleimides | |
| JPH0710836A (en) | Production of maleimide | |
| JPS63264564A (en) | Novel ether diamine and its production | |
| JPH05286907A (en) | Aromatic dinitro compound, aromatic diamino compound and their production | |
| US5011955A (en) | Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis | |
| US5334733A (en) | Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis | |
| JPH0499764A (en) | Production of 4,4'-bis(maleimidophenoxy) biphenyl |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |