JPH03292307A - Bismaleimide compound and production of polyimide - Google Patents
Bismaleimide compound and production of polyimideInfo
- Publication number
- JPH03292307A JPH03292307A JP2093941A JP9394190A JPH03292307A JP H03292307 A JPH03292307 A JP H03292307A JP 2093941 A JP2093941 A JP 2093941A JP 9394190 A JP9394190 A JP 9394190A JP H03292307 A JPH03292307 A JP H03292307A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- polyimide
- tables
- bismaleimide
- compound
- 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.)
- Pending
Links
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 20
- -1 Bismaleimide compound Chemical class 0.000 title claims abstract description 17
- 229920001721 polyimide Polymers 0.000 title claims abstract description 15
- 239000004642 Polyimide Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 7
- 125000001033 ether group Chemical group 0.000 abstract description 2
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 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 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- AYKMXKNVEUMLFQ-UHFFFAOYSA-N 2-(1,8-naphthyridin-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C(C=CC=N2)C2=N1 AYKMXKNVEUMLFQ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000006210 cyclodehydration reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YUZSJKBFHATJHV-UHFFFAOYSA-N 2-[4-[2-[4-(2-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C(=CC=CC=3)N)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 YUZSJKBFHATJHV-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- MVWMJKJYAMJIEO-UHFFFAOYSA-N bicyclo[2.2.1]hept-1-ene-4,5-dicarboxylic acid Chemical compound C1C(C(O)=O)(C2)C(C(=O)O)CC2=C1 MVWMJKJYAMJIEO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
- Indole Compounds (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）
本発明は熱安定性、成型性に優れた耐熱性樹脂及びそれ
に使用されるビスマレイミド化合物に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-resistant resin with excellent thermal stability and moldability, and a bismaleimide compound used therein.
（従来の技術及びその問題点）
近年、電気・電子分野、航空機、車輌等の分野において
は、機器の高性能化、小形軽量化に伴い、耐熱性のより
優れた材料が求められている。(Prior Art and its Problems) In recent years, in the electric/electronic fields, aircraft, vehicles, and other fields, materials with better heat resistance are required as equipment becomes more sophisticated, smaller, and lighter.
従来、該分野においては、エポキシ樹脂、縮合系ポリイ
ミド樹脂等が用いられている。しかしながら、エポキシ
樹脂は機械特性、電気特性に優れているが、耐熱性は必
ずしも充分とはいえない。Conventionally, in this field, epoxy resins, condensed polyimide resins, etc. have been used. However, although epoxy resins have excellent mechanical properties and electrical properties, their heat resistance is not necessarily sufficient.
また、ポリイミド樹脂は不溶不融であるため、成型が困
難である。Moreover, since polyimide resin is insoluble and infusible, it is difficult to mold it.
成型加工性を改良したポリイミドとして、附加型のビス
マレイミド樹脂が知られている。しかしながら、従来の
ビスマレイミド樹脂を熱重合して得られる硬化樹脂は脆
いため、実用に耐えるものではなかった。また、ビスマ
レイミド硬化物の可撓性を改善するために種々のジアミ
ン化合物を配合したポリアミノビスマレイミドが実用化
された。Addition-type bismaleimide resin is known as a polyimide with improved moldability. However, cured resins obtained by thermally polymerizing conventional bismaleimide resins are brittle and cannot be put to practical use. Furthermore, polyamino bismaleimide blended with various diamine compounds has been put into practical use in order to improve the flexibility of bismaleimide cured products.
しかし、かかる方法は硬化物中にアミノ基を残存させる
ため、耐熱性を犠牲にしなければならないという欠点が
あった。However, this method has the disadvantage that heat resistance must be sacrificed because the amino groups remain in the cured product.
（問題点を解決するための手段）
本発明者らは、附加型ビスマレイミド樹脂の耐熱性、可
撓性、成型性について鋭意研究した結果、チオエーテル
基又はエーテル基を含有するビスマレイミド化合物は低
温溶融性を示し、その結果、これから得られるポリイミ
ド化合物は成型性並びに耐熱性に秀れることを見い出し
、本発明を完成させるに到った。(Means for Solving the Problems) As a result of extensive research into the heat resistance, flexibility, and moldability of addition-type bismaleimide resins, the present inventors found that bismaleimide compounds containing thioether groups or ether groups are It was discovered that the polyimide compound exhibits meltability, and as a result, the polyimide compound obtained therefrom has excellent moldability and heat resistance, leading to the completion of the present invention.
即ち、本発明は、
（１） 一般式
わされるビスマレイミド化合物であり、（２）
で表わされるビス〔（４−ノルボルネンジカルボン酸イ
ミド）フェノキシフェニル〕へキサフルオロプロパンで
あり、更に、
（３）一般式
で表わされるビスイミド化合物を附加重合するこ（Ｙの
定義は前に同し）
ヒス［４−（４−マレイミドチオフェノキシ）フェニル
〕スルホキシド（以下、ＢＭＴＰＳとも云う）、及びビ
ス［４−（４−マレイミドチオフェノキシ）フェニルコ
ケトン（以下、ＢＭＴＰＫとも云う）、並びに２，２−
ビス（４−［４−（５−ノルボルネン−２，３−ジカル
ボン酸イミド）フェノキシ）フェニル〕ヘキサフルオロ
プロパン（以下、ＢＮＰＰＰとも云う）である。That is, the present invention provides (1) a bismaleimide compound represented by the general formula, (2) bis[(4-norbornenedicarboxylic acid imido)phenoxyphenyl]hexafluoropropane, and further, (3 ) By addition polymerizing a bisimide compound represented by the general formula (the definition of Y is the same as above), his[4-(4-maleimidothiophenoxy)phenyl]sulfoxide (hereinafter also referred to as BMTPS) and bis[4- (4-maleimidothiophenoxy)phenylkoketone (hereinafter also referred to as BMTPK), and 2,2-
It is bis(4-[4-(5-norbornene-2,3-dicarboxylic imido)phenoxy)phenyl]hexafluoropropane (hereinafter also referred to as BNPPP).
上記一般式ＣＩ）のビスマレイミド化合物の製法は何ん
ら制限されないか、一般に、まず下記−般式〔■〕で表
わされる芳香族
で表わされる
（Ｙの定義は前に同し）
ジアミンと無水マレイン酸とから、下記一般式（ＩＩＩ
］で表わされる芳香族マレアミック酸を製造・・・・・
・・・・・・・（ＩＩＩ）
（Ｙの定義は前に同じ）
し、次いで、該芳香族マレアミック酸を脱水環化して製
造する。The method for producing the bismaleimide compound of the above general formula CI) is not limited in any way; in general, first, it is represented by an aromatic group represented by the following general formula [■] (the definition of Y is the same as above), a diamine and anhydride. From maleic acid, the following general formula (III
] Production of aromatic maleamic acid represented by...
(III) (The definition of Y is the same as above) and then the aromatic maleamic acid is produced by cyclodehydration.
芳香族マレアミック酸の製造において、一般に芳香族ジ
アミン１モルに対し、無水マレイン酸２〜３モル、好ま
しくは２〜２．５モルを、乾燥溶媒中で、０〜６０℃、
２〜１０時間反応させる。溶媒としては、例えば、アセ
トン、アセトニトリル、Ｎ。In the production of aromatic maleamic acid, generally 2 to 3 moles, preferably 2 to 2.5 moles, of maleic anhydride are added to 1 mole of aromatic diamine in a dry solvent at 0 to 60°C.
Allow to react for 2 to 10 hours. Examples of the solvent include acetone, acetonitrile, and N.
Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、Ｎ
−メチルピロリドン等の非プロトン性極性溶媒が挙げら
れる。N-dimethylformamide, dimethyl sulfoxide, N
-Aprotic polar solvents such as methylpyrrolidone.
次いで、上記反応溶液中に脱水環化剤を添加し、４０〜
１００°Ｃで加熱攪拌して脱水環化反応を行う。Next, a dehydrating cyclizing agent was added to the above reaction solution, and 40~
The dehydration cyclization reaction is carried out by heating and stirring at 100°C.
脱水環化剤としては通常、一般式（ＩＩＩ）の芳香族マ
レアミック酸１モルに対し、無水酢酸２〜ＩＯモル、無
水酢酸ナトリウム２モルを用いる。As the dehydrating cyclizing agent, 2 to IO mol of acetic anhydride and 2 mol of sodium acetate anhydride are usually used per 1 mol of the aromatic maleamic acid of general formula (III).
得られた溶液を、・５０〜３００重量倍の水中に投入し
て生した沈澱物を減圧下、３０〜７０℃で乾燥して、本
発明のビスマレイミド化合物の粗生成物を得る。The obtained solution is poured into 50 to 300 times the weight of water, and the resulting precipitate is dried at 30 to 70°C under reduced pressure to obtain a crude product of the bismaleimide compound of the present invention.
得られた粗生成物は、必要に応じて再結晶又は逆相カラ
ムを用いた液体クロマトグラフィー等により精製を行い
、後の重合に供する。The obtained crude product is purified, if necessary, by recrystallization or liquid chromatography using a reversed phase column, and then used for subsequent polymerization.
本発明のＢＮＰＰＰの製造法も何んら制限されないが、
一般に、ビス［４−（４−アミノフェノキシ）フェニル
〕へキサフルオロプロパンと５−ルポルネンー２，３−
ジカルボン酸無水物を反応させて得たアミック酸化合物
を脱水環化して製造する。原料仕込比、溶媒、脱水環化
剤、その他の反応条件等は前記一般式［Ｉ）のビスマレ
イミド化合物の製造に用いられたものと同様である。Although the method for producing BNPPPP of the present invention is not limited in any way,
Generally, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and 5-luporne-2,3-
It is produced by cyclodehydration of an amic acid compound obtained by reacting a dicarboxylic anhydride. The raw material charging ratio, solvent, dehydrating cyclization agent, other reaction conditions, etc. are the same as those used in the production of the bismaleimide compound of general formula [I].
本発明のポリイミドは、下記一般式〔■〕によって表わ
されるビスマレイミド化合物を附加重合することによっ
て得られる。The polyimide of the present invention can be obtained by addition polymerization of a bismaleimide compound represented by the following general formula [■].
（式中のＸ、Ａ、及びＺの定義は前に同じ）具体的ポリ
イミドとしては、ポリビス［４−（４マレイミドチオフ
エノキシ）フェニル］スルホキシド、ポリビスＣ４−（
４−マレイミドチオフェノキシ）フェニルコケトン、ポ
リ２，２−ビス［４−（４−マレイミドフェノキシ）フ
ェニル〕へキサフルオロプロパン、ポリビス〔４〜（４
−マレイミドチオフェノキシ）フェニル〕スルホン、ポ
リ２，２−ビス〔４ｆ ４−（５−ノルボルネン−２，
３−ジカルボン酸イミド）フェノキシ）フェニル〕へキ
サフルオロプロパン等が挙げられる。又、上記一般式［
ＩＶ）のビスマレイミド化合物を互に共重合させたポリ
イミドも本発明に含まれる。(The definitions of X, A, and Z in the formula are the same as before.) Specific polyimides include polybis[4-(4maleimidothiophenoxy)phenyl]sulfoxide, polybisC4-(
4-Maleimidothiophenoxy)phenyl coketone, poly2,2-bis[4-(4-maleimidophenoxy)phenyl]hexafluoropropane, polybis[4-(4
-maleimidothiophenoxy)phenyl]sulfone, poly2,2-bis[4f 4-(5-norbornene-2,
Examples include 3-dicarboxylic acid imido)phenoxy)phenyl]hexafluoropropane. In addition, the above general formula [
Polyimides obtained by copolymerizing the bismaleimide compounds of IV) with each other are also included in the present invention.
上記ポリイミドの製造に用いる附加重合について以下説
明する。本製法に用いられるビスマレイミド化合物は粉
末状で存在しており、これを直接重合すると体積収縮を
おこすので、重合前に一度溶融して緻密な固形物とした
後重合する方が好ましい。重合は通常、重合温度２００
〜２５０℃、窒素、アルゴン等の不活性ガス雰囲気下で
塊状重合で行う。必要に応じて、過酸化ベンゾイル、ア
ゾビスイソブチロニトリル等の重合開始剤を添加したり
、３０〜７０ ｋｇ ／ ｃｒｄの加圧下に行う方法も
採用される。Addition polymerization used to produce the above polyimide will be explained below. The bismaleimide compound used in this production method exists in the form of a powder, and direct polymerization causes volumetric shrinkage, so it is preferable to melt the compound once to form a dense solid before polymerization and then polymerize it. Polymerization is usually carried out at a polymerization temperature of 200
Bulk polymerization is carried out at ~250°C under an inert gas atmosphere such as nitrogen or argon. If necessary, a method in which a polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile is added or a pressure of 30 to 70 kg/crd is applied is also adopted.
重合硬化物の精製は特に行なわず、以下の測定に供する
。尚、本発明のポリイミドの製造において、その目的を
損なわない範囲において他の附加共重合可能な不飽和化
合物を存在させて重合させてもよい。The polymerized cured product was not particularly purified and was used for the following measurements. In the production of the polyimide of the present invention, other unsaturated compounds capable of addition copolymerization may be present and polymerized within a range that does not impair the purpose.
物性評価は、熱重量分析（Ｔ Ｇ Ａ）による熱分解開
始温度と、ボックス型電気炉（静止大気雰囲気）による
エージング試験（２５０°Ｃ）で行った。ＴＧＡは昇温
速度ｌＯ°Ｃ／ｌＴｌ１ｎで加熱し、重量減少が始まる
温度を熱分解開始温度とした。エージング試験は、エー
ジング前後の試量の重量変化を測定し、試料の耐酸化性
の尺度とした。又、２５０℃、２００時間のエージング
後、試料にクラックが発生しているかどうかを目視で確
認した。The physical properties were evaluated by determining the thermal decomposition start temperature by thermogravimetric analysis (TGA) and by an aging test (250°C) using a box-type electric furnace (static air atmosphere). TGA was heated at a temperature increase rate of lO°C/lTl1n, and the temperature at which weight loss began was defined as the thermal decomposition start temperature. In the aging test, the change in weight of the sample before and after aging was measured, and this was used as a measure of the oxidation resistance of the sample. Further, after aging at 250° C. for 200 hours, it was visually confirmed whether or not cracks had occurred in the sample.
（効 果）
従来のビスマレイミド化合物である１、３−）リレンビ
スマレイミド（融点１６５°Ｃ）や、２，２〜ビス（４
−マレイミドフェニル）へキサフルオロプロパン（融点
２４７℃）が高温溶融性を有するのに対し、本発明のビ
スマレイミド化合物は低温溶融性を有するために硬化前
に低温で成型可能であり、この成型体を附加重合するこ
とにより得られた硬化樹脂は耐熱性が大であると共に加
熱、冷却によってクラックの発生が起こりにくいという
性質もあわせ有する。(Effect) Conventional bismaleimide compounds such as 1,3-)rylene bismaleimide (melting point 165°C) and 2,2-bis(4-)
-maleimidophenyl)hexafluoropropane (melting point: 247°C) has high-temperature melting properties, whereas the bismaleimide compound of the present invention has low-temperature melting properties, so it can be molded at low temperatures before curing, and this molded product The cured resin obtained by addition polymerization has high heat resistance and also has the property of being less likely to generate cracks when heated or cooled.
以下、実施例により本発明の詳細な説明するが、これら
実施例により何んら制限されるものではな実施例１
共沸脱水管、かく拌モータを取り付けたＩＩ四日フラス
コに、ジメチルアセトアミド４００−を入れ、４−アミ
ノチオフェノール３３ｇ、ならびに無水炭酸カリウム５
１．８ｇを溶解する。さらに、トルエン２００ｄ、水１
０−を加え、窒素気流下で、加熱かくはんを行い、６時
間脱水を行う。最後に液温か１５０°Ｃになるまで加熱
を行い、トルエンを留去する。Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited in any way. -, 33g of 4-aminothiophenol, and 5g of anhydrous potassium carbonate.
Dissolve 1.8g. Furthermore, 200 d of toluene, 1 d of water
0- is added, heated and stirred under a nitrogen stream, and dehydrated for 6 hours. Finally, heating is performed until the liquid temperature reaches 150°C, and toluene is distilled off.
溶液は室温にもどるまで放冷し、４−クロロフェニルス
ルホキシド２５ｇをジメチルアセトアミド１００７ｎｌ
に溶解した溶液を徐々に加える。溶液は１５０°Ｃで２
時間加熱かくはんを行う。得られた反応溶液を３１の水
にあけ、得られた沈澱をろ過によって回収した。得られ
た粉末は、６０℃で２４時間減圧乾燥を行った。The solution was allowed to cool until it returned to room temperature, and 25 g of 4-chlorophenylsulfoxide was added to 1007 nl of dimethylacetamide.
Gradually add the solution dissolved in The solution was heated to 2 at 150°C.
Heat and stir for an hour. The resulting reaction solution was poured into 31ml of water, and the resulting precipitate was collected by filtration. The obtained powder was dried under reduced pressure at 60° C. for 24 hours.
前述の乾燥粉末１５ｇをアセトン３００−に溶解し、窒
素気流下でかくはんしてお（。無水マレイン酸７ｇをア
セトン５０−に溶解した溶液を、前述の溶液に加え、６
時間、室温でかくはんを行う。Dissolve 15 g of the dry powder described above in 300 °C of acetone and stir under a nitrogen stream.A solution of 7 g of maleic anhydride dissolved in 50 °C of acetone was added to the above solution, and
Stir at room temperature for an hour.
得られた懸濁溶液に、無水酢酸２０ｇを、無水酢酸ナト
リウム５ｇを加え、６０°Ｃで７時間加熱かくはんする
。To the obtained suspension solution, 20 g of acetic anhydride and 5 g of anhydrous sodium acetate are added, and the mixture is heated and stirred at 60° C. for 7 hours.
得られた溶液を、１１の水にあけ、得られた沈澱をろ過
によって回収した。得られた粉末は、６０℃で２４時間
減圧乾燥を行った後、逆相液体クロマトグラフにより、
目的物を単離精製した。収率は７４％、融点は９６℃で
あった。The obtained solution was poured into 11 water, and the obtained precipitate was collected by filtration. The obtained powder was dried under reduced pressure at 60°C for 24 hours, and then subjected to reverse phase liquid chromatography.
The target product was isolated and purified. The yield was 74% and the melting point was 96°C.
得られた上記化合物の赤外吸収スペクトル分析、並びに
’Ｈ−ＮＭＲ分析を行い、本化合物をビス（４−（４マ
レイミドチオフエノキシ）フェニル〕スルホキシドと同
定した。各スペクトルデータを第１図。The resulting compound was subjected to infrared absorption spectrum analysis and 'H-NMR analysis, and the present compound was identified as bis(4-(4maleimidothiophenoxy)phenyl]sulfoxide.Each spectral data is shown in Figure 1. .
第２図に示す。Shown in Figure 2.
実施例２
４−クロロフェニルスルホキシドの代わりに、４クロロ
フエニルケトンを用いること以外は実施例１と同様に合
成を行った。収率は８４％、融点は８４℃であった。Example 2 Synthesis was carried out in the same manner as in Example 1 except that 4-chlorophenyl ketone was used instead of 4-chlorophenyl sulfoxide. The yield was 84% and the melting point was 84°C.
得られた化合物の赤外吸収スペクトル分析、並びに’Ｈ
−ＮＭＲ分析を行い、本化合物をビス（４−（４−マレ
イミドチオフェノキシ）フェニルコケトンと同定した。Infrared absorption spectrum analysis of the obtained compound and 'H
-NMR analysis was performed and the present compound was identified as bis(4-(4-maleimidothiophenoxy)phenylkoketone).
各スペクトルデータを第３図、第４図に示す。Each spectrum data is shown in FIGS. 3 and 4.
実施例３
ビス〔４−（アミノフェノキシ）フェニル〕へキサフル
オロプロパン（セントラル硝子社製）２５ｇをアセトン
３００７ｎｌに溶解し、窒素気流下でかくはんしておく
。Example 3 25 g of bis[4-(aminophenoxy)phenyl]hexafluoropropane (manufactured by Central Glass Co., Ltd.) is dissolved in 3007 nl of acetone and stirred under a nitrogen stream.
シス−５−ノルボルネン−２，３−ジカルボン酸無水物
２４ｇをアセトン１００−に溶解した溶液を前述の溶液
に加え、６時間室温でかくはんを行う。該溶液に無水酢
酸３０ｇ、無水酢酸ナトリウム８ｇを加え、６０°Ｃて
７時間加熱かくはんを行った。A solution of 24 g of cis-5-norbornene-2,3-dicarboxylic anhydride dissolved in 100% acetone is added to the above solution, and stirred at room temperature for 6 hours. 30 g of acetic anhydride and 8 g of anhydrous sodium acetate were added to the solution, and the mixture was heated and stirred at 60° C. for 7 hours.
室温に放冷した後溶液を１１の水にあけ、沈澱をろ別し
た。得られた粉末は６０℃、２４時間減圧乾燥を行った
後、逆相液体クロマトグラフにより単離精製を行った。After cooling to room temperature, the solution was poured into 11 portions of water, and the precipitate was filtered off. The obtained powder was dried under reduced pressure at 60° C. for 24 hours, and then isolated and purified using reverse phase liquid chromatography.
収率は７０％、融点は１６５℃であった。The yield was 70% and the melting point was 165°C.
得られた上記化合物の赤外吸収スペクトル分析、並びに
’ｌ（−ＮＭＲ分析を行い、本化合物を２，２−ビスＣ
４−［４−（５−ノルボルネン−２，３〜ジカルボン酸
イミド）フェノキシ） フェニル〕ヘキサフルオロプロ
パンと同定した。各スペクトルデータを第５図。The resulting compound was subjected to infrared absorption spectrum analysis and 'l(-NMR analysis), and this compound was identified as 2,2-bisC
It was identified as 4-[4-(5-norbornene-2,3-dicarboxylic acid imido)phenoxy)phenyl]hexafluoropropane. Figure 5 shows each spectrum data.
第６図に示す。It is shown in FIG.
（／ｌごリイミドら製Ｊす
■化合物）を、各々 １００■、直径６ ｍｍ、高さ４
＋ｎｍのアルミセルに詰め、Ｎ！気流下、２５０℃、
２時間硬化反応を行った後、硬化物をセルから取り出し
、前記物性測定を行った。結果もあわせて表２に示す。(Jsu compound manufactured by Gorimido et al.), each 100 mm, diameter 6 mm, height 4
Packed into a +nm aluminum cell, N! Under air flow, 250℃,
After carrying out the curing reaction for 2 hours, the cured product was taken out from the cell and the physical properties were measured. The results are also shown in Table 2.
実施例８
実施例３で合成した２、２−ビス（４−［４−（５−ノ
ルボルネン−２，３−ジカルボン酸イミド）フェノキシ
）フェニル〕ヘキサフルオロプロパン１００■ヲ直径６
ｍｍ、高さ４ｍｍのアルミセルに詰め、５０ｋｇ ／
ｃｒｉＮ２雰囲気、３００℃の加圧加熱条件下で２時間
硬化反応を行った以外は実施例４〜７と同様に行った。Example 8 2,2-bis(4-[4-(5-norbornene-2,3-dicarboxylic imido)phenoxy)phenyl]hexafluoropropane synthesized in Example 3 100cm diameter 6
packed in aluminum cells with a height of 4 mm and a weight of 50 kg/
The curing reaction was carried out in the same manner as in Examples 4 to 7, except that the curing reaction was carried out for 2 hours under pressure and heating conditions of 300° C. in a criN2 atmosphere.
結果を表２に示す。The results are shown in Table 2.
比較例１
ビスマレイミド化合物として１．３−）リレンビスマレ
イミド（融点１６５°Ｃ）を用いた以外は実施例４〜７
と同様に行った。結果を表２に示す。Comparative Example 1 Examples 4 to 7 except that 1.3-)rylene bismaleimide (melting point 165°C) was used as the bismaleimide compound.
I did the same thing. The results are shown in Table 2.
手 続 補 正 書 （ 方 式 ） ％式％ 事件の表示 平成２年特許願８９３９４１号 ２、発明の名称 ビスマレイミド化合物及びポリイミド の製造方法 ３、補正をする者 事件との関係 特許出鳳人 住 所 山口県徳山市御影町１番１４＋ 〆。hand Continued Supplementary Positive book ( direction formula ) %formula% Display of incidents 1990 Patent Application No. 893941 2. Name of the invention Bismaleimide compounds and polyimides manufacturing method 3. Person who makes corrections Relationship to the incident Patent issue Address: 1-14+ Mikage-cho, Tokuyama City, Yamaguchi Prefecture.
連絡先 東京都港区西新橋１丁目４番５号徳山１達株
式会社 東京本部
特許情報部
電 話 ５９７−５１１１
補正命合の日付 平成２年６月２９日５、補正の
対象
明細書の「図面の簡単な説明」σフ項及び同梱
６ 補正の内容
σ）明細書第１７頁第１行目の「特許出願人徳山曹達株
式会肚」の前に欧文を挿入する。Contact information: Tokuyama 1-4-5 Nishi-Shinbashi, Minato-ku, Tokyo Tokyo Headquarters Patent Information Department Telephone number: 597-5111 Date of order for amendment: June 29, 1990 5. "Brief explanation of the drawings" σ Section 6 and Enclosure 6 Contents of the amendment σ) Insert the European language before "Patent applicant Tokuyama Soda Co., Ltd." in the first line of page 17 of the specification.
Claims (1)
は▲数式、化学式、表等があります▼基を示す。）で表
わされるビスマレイミド化合物。 ２、 ▲数式、化学式、表等があります▼ で表わされる２，２−ビス〔４−｛４−（５−ノルボル
ネン−２，３−ジカルボン酸イミド）フェノキシ｝フェ
ニル〕ヘキサフルオロプロパン。 ３、一般式 ▲数式、化学式、表等があります▼ 〔式中、Ｘは−Ｏ−基、又は−Ｓ−基を示し、Ａは▲数
式、化学式、表等があります▼、及び▲数式、化学式、
表等があります▼ から選ばれる基を示し、Ｚは−Ｃ＝Ｃ−基、又は▲数式
、化学式、表等があります▼基を示す。〕 で表わされるビスイミド化合物を附加重合することを特
徴とするポリイミドの製造方法。[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Y is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups A bismaleimide compound represented by 2. 2,2-bis[4-{4-(5-norbornene-2,3-dicarboxylic imido)phenoxy}phenyl]hexafluoropropane, which is represented by ▲Mathematical formulas, chemical formulas, tables, etc.▼. 3. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Chemical formula,
There are tables, etc. ▼ Indicates a group selected from ▼ where Z is a -C=C- group, or ▲ Numerical formulas, chemical formulas, tables, etc. ▼. ] A method for producing polyimide, which comprises addition-polymerizing a bisimide compound represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2093941A JPH03292307A (en) | 1990-04-11 | 1990-04-11 | Bismaleimide compound and production of polyimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2093941A JPH03292307A (en) | 1990-04-11 | 1990-04-11 | Bismaleimide compound and production of polyimide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03292307A true JPH03292307A (en) | 1991-12-24 |
Family
ID=14096461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2093941A Pending JPH03292307A (en) | 1990-04-11 | 1990-04-11 | Bismaleimide compound and production of polyimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03292307A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002088120A (en) * | 2000-03-16 | 2002-03-27 | Toray Ind Inc | Poly(alicyclic olefin) |
| CN100360504C (en) * | 2005-12-22 | 2008-01-09 | 上海交通大学 | Sulfur-containing, polymerizable benzophenone photoinitiator and preparation method thereof |
| CN100372832C (en) * | 2006-04-20 | 2008-03-05 | 上海交通大学 | Diamine contg. sulphur and diphenyl ketone structure, and its prepn. method |
| CN100427461C (en) * | 2006-03-30 | 2008-10-22 | 上海交通大学 | Polymerisable benzophenone photoinitiator and its preparing method |
| CN102942564A (en) * | 2012-11-20 | 2013-02-27 | 沈阳航空航天大学 | Asymmetric bismaleimide containing 1, 3, 4-oxadiazole structure and preparation method thereof |
-
1990
- 1990-04-11 JP JP2093941A patent/JPH03292307A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002088120A (en) * | 2000-03-16 | 2002-03-27 | Toray Ind Inc | Poly(alicyclic olefin) |
| CN100360504C (en) * | 2005-12-22 | 2008-01-09 | 上海交通大学 | Sulfur-containing, polymerizable benzophenone photoinitiator and preparation method thereof |
| CN100427461C (en) * | 2006-03-30 | 2008-10-22 | 上海交通大学 | Polymerisable benzophenone photoinitiator and its preparing method |
| CN100372832C (en) * | 2006-04-20 | 2008-03-05 | 上海交通大学 | Diamine contg. sulphur and diphenyl ketone structure, and its prepn. method |
| CN102942564A (en) * | 2012-11-20 | 2013-02-27 | 沈阳航空航天大学 | Asymmetric bismaleimide containing 1, 3, 4-oxadiazole structure and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5681967A (en) | Phenylethynyl phthalic anhydride | |
| US4276407A (en) | Acetylene terminated imide oligomers which melt at low temperatures | |
| US5689004A (en) | Diamines containing pendent phenylethynyl groups | |
| Liaw et al. | Synthesis and properties of new polyimides derived from 1, 1-bis [4-(4-aminophenoxy) phenyl] cyclododecane | |
| Liaw et al. | Highly organosoluble and flexible polyimides with color lightness and transparency based on 2, 2‐bis [4‐(2‐trifluoromethyl‐4‐aminophenoxy)‐3, 5‐dimethylphenyl] propane | |
| JPS59113034A (en) | Polyamide-imide and manufacture | |
| Kim et al. | Synthesis of soluble poly (ether imides) from bis (ether anhydrides) containing bulky substituents | |
| JPH03275669A (en) | New bisphenols containing imide ring and production thereof | |
| Chen et al. | The synthesis and characterization of fluorinated polyimides derived from 2′-methyl-1, 4-bis-(4-amino-2-trifluoromethylphenoxy) benzene and various aromatic dianhydrides | |
| US4845167A (en) | Condensation polyimides containing 1,1,1-triaryl-2,2,2-trifluoroethane structures | |
| JPH03292307A (en) | Bismaleimide compound and production of polyimide | |
| Sugioka et al. | Synthesis of novel poly (thioether‐naphthalimide) s that utilize hydrazine as the diamine | |
| CA1074492A (en) | Crosslinkable polymers | |
| US5122617A (en) | Tetracarboxylic acid dianhydrides | |
| JPH0215084A (en) | Fluorine-containing pyromellitic dianhydride and preparation thereof | |
| US5112989A (en) | Process for producing unsaturated mono and dicarboxylic acid imide compound | |
| US5118781A (en) | Poly(1,3,4-oxadiozoles) via aromatic nucleophilic displacement | |
| JP2651219B2 (en) | Method for producing curable resin containing imide ring | |
| JP2628374B2 (en) | Bismaleimide compound and method for producing the same | |
| EP0314766B1 (en) | Method for making thianthrene dianhydride and polyimides obtained therefrom | |
| JP2698384B2 (en) | Fluorine-containing pyromellitic anhydride and method for producing the same | |
| JPS63255262A (en) | Bismaleimide and production thereof | |
| JPH0586780B2 (en) | ||
| JPH0717600B2 (en) | Bismaleimide compound and method for producing the same | |
| WO1981001293A1 (en) | Acetylene terminated imide oligomers having improved solubilities and lower melting points |