JPH0446155A - 4-(hydroxyphenoxy)phenylmaleimide and production thereof - Google Patents
4-(hydroxyphenoxy)phenylmaleimide and production thereofInfo
- Publication number
- JPH0446155A JPH0446155A JP2154017A JP15401790A JPH0446155A JP H0446155 A JPH0446155 A JP H0446155A JP 2154017 A JP2154017 A JP 2154017A JP 15401790 A JP15401790 A JP 15401790A JP H0446155 A JPH0446155 A JP H0446155A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- phenylmaleimide
- hydroxyphenoxy
- maleic anhydride
- acid
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- DVRINAVHRSJELP-UHFFFAOYSA-N OC1=C(OC2=CC=C(C=C2)C=2C(=O)NC(C2)=O)C=CC=C1 Chemical compound OC1=C(OC2=CC=C(C=C2)C=2C(=O)NC(C2)=O)C=CC=C1 DVRINAVHRSJELP-UHFFFAOYSA-N 0.000 title 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 28
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 15
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003607 modifier Substances 0.000 abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002798 polar solvent Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 abstract 1
- 239000007859 condensation product Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- -1 3- Hydroxyphenoxyphenylmaleimide Chemical compound 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- 239000006227 byproduct Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- MFOZEMMOSBIWMZ-UHFFFAOYSA-N 1-[4-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(N2C(C=CC2=O)=O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 MFOZEMMOSBIWMZ-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- WKURVXXDGMYSDP-UHFFFAOYSA-N 2-propyl-aniline Chemical compound CCCC1=CC=CC=C1N WKURVXXDGMYSDP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 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
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000001953 recrystallisation Methods 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、主に樹脂改質剤として有用なヒドロキシ基を
有する新規なモノマレイミド化合物およびその製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel monomaleimide compound having a hydroxy group that is mainly useful as a resin modifier and a method for producing the same.
本発明の４− （３−（または４−）（以下、単に３−
（４−）と略記）ヒドロキシフェノキシフフェニルマレ
イミドは、モノマレイミド化合物として典型的なフェニ
ルマレイミド類と同様に、樹脂改質剤として利用できる
。4- (3- (or 4-) (hereinafter simply 3-
Hydroxyphenoxyphenylmaleimide (abbreviated as (4-)) can be used as a resin modifier in the same way as typical phenylmaleimides as monomaleimide compounds.
例えば、ポリスチレン樹脂等における耐熱性向上を目的
とする利用方法がある。一方、４−〔３−（４−）ヒド
ロキシフェノキシフフェニルマレイミドのフェノールの
フェノール構造部分を利用したフェノール樹脂の改質も
考えられる。For example, there is a method of using it for the purpose of improving heat resistance in polystyrene resin and the like. On the other hand, modification of the phenol resin using the phenol structural part of the phenol of 4-[3-(4-)hydroxyphenoxyphenylmaleimide is also considered.
このようなフェノール構造部分を持つマレイミド化合物
としては、２−（４−ヒドロキシフェニル） −２−（
４’−マレイミドフェニル）プロパンが知られている。As a maleimide compound having such a phenolic structure moiety, 2-(4-hydroxyphenyl)-2-(
4'-maleimidophenyl)propane is known.
しかしながら、このマレイミド化合物においては、その
分子内にあるイソプロピリデン基の熱安定性が悪いため
に耐熱性や長期間の使用における安定性等で改良が求め
られている０本発明の４＝（３−（４−）ヒドロキシフ
ェノキシュフェニルマレイミドは、結合基がエーテル結
合であり、これを使用して樹脂を得た場合、結合基の安
定性は十分である。However, in this maleimide compound, since the isopropylidene group in the molecule has poor thermal stability, improvements are required in terms of heat resistance and stability during long-term use. -(4-)Hydroxyphenoxyphenylmaleimide has an ether bond as a bonding group, and when a resin is obtained using this, the stability of the bonding group is sufficient.
従来、ヒドロキシ基を有するモノマレイミド化合物の製
造例は、２−（４−ヒドロキシフェニル）−２−（４’
−アミノフェニル〕プロパンと無水マレイン酸から得ら
れるマレイミド酸を無水酢酸等で脱水閉環反応させる方
法が提案されている（特開昭５５−１４９２５３）。Conventionally, an example of manufacturing a monomaleimide compound having a hydroxy group is 2-(4-hydroxyphenyl)-2-(4'
A method has been proposed in which maleimide acid obtained from -aminophenyl]propane and maleic anhydride undergoes a dehydration ring-closing reaction with acetic anhydride or the like (Japanese Unexamined Patent Publication No. 149253/1983).
この方法では、原料化合物が水酸基を有しているために
アセチル化物を生成するためか、あるいは水酸基が無水
マレイン酸の二重結合への付加反応を起こすためか、副
生成物が多く、目的とするマレイミドの純度および収率
が低い欠点がある。In this method, there are many by-products, perhaps because the raw material compound has a hydroxyl group to produce an acetylated product, or because the hydroxyl group causes an addition reaction to the double bond of maleic anhydride. The drawback is that the purity and yield of maleimide produced is low.
Ｃ発明が解決しようとする課題〕
本発明の目的は、樹脂改質剤として使用した場合、樹脂
の耐熱性はもちろんのこと長期間の安定性能を十分満足
させ、なおかつ、高収率で安価に提供できるようなヒド
ロキシ基を有する新規モノマレイミド化合物を提供する
ことにある。C Problems to be Solved by the Invention] The purpose of the present invention is to provide a resin modifier that, when used as a resin modifier, sufficiently satisfies not only the heat resistance of the resin but also the long-term stable performance, while also achieving high yield and low cost. The object of the present invention is to provide a novel monomaleimide compound having a hydroxyl group.
本発明者らは、上記の目的を達成すべく鋭意検討した結
果、本発明を完成するに至った。The present inventors have completed the present invention as a result of intensive studies to achieve the above object.
すなわち、本発明は一般式（１）
で表される４−［３−（４−）ヒドロキシフェノキシュ
フェニルマレイミド、および３−（または４−）ヒドロ
キシ−４”−アミノジフェニルエーテルと無水マレイン
酸を水と共沸可能な有機溶剤中、酸触媒の存在下で脱水
閉環反応させることを特徴とする４−（３−（４−）ヒ
ドロキシフェノキシュフェニルマレイミドの製造方法で
ある。That is, the present invention provides 4-[3-(4-)hydroxyphenoxyphenylmaleimide represented by the general formula (1), 3-(or 4-)hydroxy-4''-aminodiphenyl ether, and maleic anhydride in hydrated form. 4-(3-(4-)hydroxyphenoxphenylmaleimide) is a method for producing 4-(3-(4-)hydroxyphenoxphenylmaleimide), which is characterized by carrying out a dehydration ring-closing reaction in an organic solvent capable of azeotroping with 4-(3-(4-)hydroxyphenoxphenylmaleimide) in the presence of an acid catalyst.
本発明のヒドロキシ基を有する新規なモノマレイミド化
合物は、結合基がエーテル結合より成り、フェノール性
ヒドロキシ基はエーテル結合に対し、それぞれメタ位と
バラ位である。In the novel monomaleimide compound having a hydroxy group of the present invention, the bonding group consists of an ether bond, and the phenolic hydroxy group is at the meta position and the rose position, respectively, with respect to the ether bond.
従って、これを使用して樹脂を得た場合、結合基の安定
性は十分であり、耐熱性はもとより長期間の信軌性に十
分耐え得ると期待できる。また、エーテル結合により樹
脂としての柔軟性や加工性は申し分ないと予想される。Therefore, when a resin is obtained using this, the stability of the bonding group is sufficient, and it can be expected that it will have sufficient heat resistance and long-term reliability. Furthermore, it is expected that the resin will have excellent flexibility and processability due to the ether bond.
一方、本発明のモノマレイミド化合物は、従来から知ら
れている２−（４−ヒドロキシフェニル）−２−（４’
−アミノフェニル）プロパンに比べ、幾分低融点である
ため、樹脂改質剤として使用する場合、樹脂との配合あ
るいは相溶性等で有利である。On the other hand, the monomaleimide compound of the present invention is a conventionally known 2-(4-hydroxyphenyl)-2-(4'
Since it has a somewhat lower melting point than (aminophenyl)propane, it is advantageous in terms of blending and compatibility with resins when used as a resin modifier.
次に、本発明の製造方法を説明する。Next, the manufacturing method of the present invention will be explained.
本発明の方法で使用される原料は、３−（または４−）
ヒドロキシ−４゛−アミノジフェニルエーテルと無水マ
レイン酸である。The raw materials used in the method of the present invention are 3-(or 4-)
They are hydroxy-4'-aminodiphenyl ether and maleic anhydride.
３−（または４−）ヒドロキシ−４゛−アミノジフェニ
ルエーテルは、レゾルシンまたはハイドロキノンとｐ−
クロルニトロベンゼンを塩基の存在下、非プロトン性極
性溶剤１中で縮合後、還元することにより製造されてい
る（例えば、独国公開特許第２１５７７８１．２８４７
６６２ 、ヨー口・ンバ特許第３５６２号）。3-(or 4-)hydroxy-4'-aminodiphenyl ether can be combined with resorcinol or hydroquinone and p-
It is produced by condensing chlornitrobenzene in an aprotic polar solvent 1 in the presence of a base and then reducing it (for example, German Published Patent Application No. 2157781.2847
662, Yoguchi-Nba Patent No. 3562).
レゾルシンを原料とした場合、３−ヒドロキシ−４゛−
アミノジフェニルエーテル、ハイドロキノンを原料とし
た場合は４−ヒドロキシ−４゛−アミノジフェニルエー
テルが製造される。When resorcinol is used as a raw material, 3-hydroxy-4゛-
When aminodiphenyl ether and hydroquinone are used as raw materials, 4-hydroxy-4'-aminodiphenyl ether is produced.
無水マレイン酸の使用量は、３−（または４−）ヒドロ
キシ−４″−アミノジフェニルエーテル１モルに対して
１．０〜１．５モルであり、好ましくは１．０５〜１．
３モル用いるのが良い。The amount of maleic anhydride used is 1.0 to 1.5 mol, preferably 1.05 to 1.5 mol, per 1 mol of 3-(or 4-)hydroxy-4''-aminodiphenyl ether.
It is better to use 3 moles.
無水マレイン酸に対しアミン化合物を過剰に使用した場
合には、過剰量の該アミン化合物が生成した４〜Ｃ３−
＜４−）ヒドロキシフェノキシュフェニルマレイミドに
付加し、副生成物を生成することがあるため好ましくな
い。When the amine compound is used in excess with respect to maleic anhydride, the excess amount of the amine compound produces 4-C3-
<4-) Hydroxyphenoxy is not preferred because it may add to phenylmaleimide and produce by-products.
本発明に用いられる酸触媒は硫酸、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酸
、Ｐ−）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、トリフルオル酢酸算のハ
ロゲン化カルボン酸等が使用され、特に硫酸、ｐ−）ル
エンスルホン酸が好適である。Acid catalysts used in the present invention include mineral acids such as sulfuric acid and phosphoric acid, heteropolyacids such as phosphotungstic acid and phosphomolybdic acid, organic sulfonic acids such as P-)luenesulfonic acid and methanesulfonic acid, trichloroacetic acid, and trifluoroacetic acid. Halogenated carboxylic acids such as acetic acid are used, and sulfuric acid and p-)luenesulfonic acid are particularly preferred.
これらの酸触媒は種類によっても異なるが、通常無水マ
レイン酸、アミン化合物との合計重量当り０．５〜５重
量％の量で使用することが好ましい。Although these acid catalysts vary depending on the type, it is usually preferable to use them in an amount of 0.5 to 5% by weight based on the total weight of maleic anhydride and the amine compound.
触媒量が０．５重量％よりも少ない場合、所望の触媒効
果が達成されず、また５重量％より多く用いたとしても
一定以上の効果は得られず、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 amount of catalyst is less than 0.5% by weight, the desired catalytic effect will not be achieved, and even if it is used in an amount greater than 5% by weight, no effect beyond a certain level will be obtained, which will not only be economically disadvantageous, but also Removal of residual catalyst becomes difficult.
本発明で用いる有機溶剤としては、脱水閉環反応で生成
する水を共沸除去できる溶剤が良（、ベンゼン、トルエ
ン、キシレン、メシチレン、クロルベンゼン等が挙げら
れる。使用量は反応を円滑に行う上から無水マレイン酸
に対して３〜１０倍量（重量比）用いるのが良い。また
、本発明の方法において、反応を円滑に進行せしめるた
めに非プロトン性極性溶剤を併用してもよい、この非プ
ロトン性極性溶剤としては、Ｎ、Ｎ−ジメチルアセトア
ミド、Ｎ１Ｎ−ジメチルホルムアミド、Ｎ−メチル−２
−ピロリドン、１．３−ジメチル−２−イミダゾリジノ
ン、Ｎ、Ｎ−ジエチルアセトアミド等が挙げられ、使用
量は使用するを線溶剤の重量に対して１０〜４０重量％
、好ましくは２０〜３０重蓋％用いるのが良い。The organic solvent used in the present invention is preferably a solvent that can azeotropically remove the water produced by the dehydration ring-closing reaction (e.g., benzene, toluene, xylene, mesitylene, chlorobenzene, etc.). It is preferable to use an amount of 3 to 10 times (weight ratio) to maleic anhydride.In addition, in the method of the present invention, an aprotic polar solvent may be used in combination to make the reaction proceed smoothly. As the aprotic polar solvent, N,N-dimethylacetamide, N1N-dimethylformamide, N-methyl-2
-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N-diethylacetamide, etc., and the amount used is 10 to 40% by weight based on the weight of the fibrinolyte used.
, preferably 20 to 30%.
本発明の方法における反応は、無水マレイン酸と有機溶
剤の混合液に、アミン化合物を加えて１５０℃以下、好
ましくは２０〜１．００℃で１０分以上、好ましくは０
．５〜１時間攪拌してマレアミド酸を生成させ、次いで
、得られた反応液に酸触媒および必要により非プロトン
性極性溶剤を加え、８０″Ｃ以上、好ましくは１００°
Ｃ〜１８０℃の温度範囲で加熱し、０．５〜２０時間、
好ましくは４〜８時間撹拌し、反応生成水を共沸分離す
ることによって行なうか、あるいは無水マレイン酸と有
機ＷｐＨＦＩおよび酸触媒の混合液を８０〜１８０℃の
温度範囲で加熱し、予めアミン化合物を同種の有機溶剤
または非プロトン性極性溶剤に溶解させた溶液を滴下し
ながら反応させ、生成する水を共沸分離することにょっ
て行っても良い。The reaction in the method of the present invention is carried out by adding an amine compound to a mixed solution of maleic anhydride and an organic solvent, and heating the mixture at 150°C or lower, preferably 20 to 1.00°C, for 10 minutes or more, preferably at 0.
．． Stir for 5 to 1 hour to generate maleamic acid, then add an acid catalyst and an aprotic polar solvent if necessary to the resulting reaction solution, and heat at 80"C or higher, preferably 100°C.
Heating at a temperature range of C to 180 C for 0.5 to 20 hours,
This is preferably carried out by stirring for 4 to 8 hours and azeotropically separating the water produced by the reaction, or by heating a mixture of maleic anhydride, organic WpHFI and an acid catalyst in a temperature range of 80 to 180°C to preliminarily remove the amine compound. The reaction may be carried out by dropping a solution prepared by dissolving the same type of organic solvent or an aprotic polar solvent, and then azeotropically separating the water produced.
このような条件で反応を行った後、７０〜８０°Ｃに冷
却し、温水を加え同温度で洗浄する。水層を分離後、有
機層を冷却すると黄色結晶の４−（３（４−）ヒドロキ
シフェノキン〕フェニルマレイミドが析出してくる。こ
れを濾過、乾燥後、ｆ４荊で再結晶することにより精製
することができる。After the reaction is carried out under these conditions, it is cooled to 70 to 80°C, and washed with hot water at the same temperature. After separating the aqueous layer, when the organic layer is cooled, yellow crystals of 4-(3(4-)hydroxyphenoquine) phenylmaleimide precipitate out. After filtering and drying, this is purified by recrystallization with f4 tungsten. can do.
本発明のモノマレイミド化合物を樹脂改質剤として使用
した樹脂は、耐熱性や長期間の安定性能等で優れた性質
が期待できる。また、本発明の製造方法では、原料の入
手が容易であり、高純度、高収率で４− ｒ３−（４−
）ヒドロキシフェノキシ）フェニルマレイミドが製造で
きる。A resin using the monomaleimide compound of the present invention as a resin modifier can be expected to have excellent properties such as heat resistance and long-term stability. In addition, in the production method of the present invention, raw materials are easily available, and 4-r3-(4-
) hydroxyphenoxy) phenylmaleimide can be produced.
以下、実施例により本発明の方法を更に詳細に説明する
。Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.
実施例１
攪拌器、温度計およびディーンスターク共沸蒸留トラッ
プを装着した反応容器に無水マレイン酸６０ｇ （０
，６１モル）、トルエン４８０ ｇおよび９５％硫酸２
．６ｇを装入し、攪拌下で還流温度まで加熱し、予めＮ
、Ｎ−ジメチルアセトアミド１６０ｇに３−ヒドロキシ
−４゛−アミノジフェニルエーテル１００．５ｇ（０，
５モル）を溶解した溶液を滴下ロートにより４〜５時間
で滴下し、同温度で５時間反応を行った。Example 1 60 g maleic anhydride (0
, 61 mol), 480 g toluene and 95% sulfuric acid 2
．． 6 g, heated to reflux temperature under stirring, and preliminarily
, 100.5 g of 3-hydroxy-4'-aminodiphenyl ether (0,
A solution containing 5 mol) was added dropwise through a dropping funnel over 4 to 5 hours, and the reaction was carried out at the same temperature for 5 hours.
反応終了後、反応液を７０〜８０°Ｃに冷却し、これに
温水５００ｇを加え、同温度で１時間攪拌した。After the reaction was completed, the reaction solution was cooled to 70 to 80°C, 500 g of warm water was added thereto, and the mixture was stirred at the same temperature for 1 hour.
３０分間静置後、水層を分液して除き、有機層を２０〜
３０゛Ｃまで冷却すると、黄色結晶の４−（３−ヒドロ
キシフェノキシ）フェニルマレイミドが析出した。濾過
乾燥後、トルエンで再結晶して目的物１２９ ｇ （
収率９２％）を得た。After standing still for 30 minutes, the aqueous layer was separated and removed, and the organic layer was
When cooled to 30°C, yellow crystals of 4-(3-hydroxyphenoxy)phenylmaleimide were precipitated. After filtering and drying, it was recrystallized with toluene to obtain 129 g of the target product (
A yield of 92%) was obtained.
液体クロマトグラフィーによる純度は、９９％であった
。Purity by liquid chromatography was 99%.
融点１２７〜１２９°Ｃ
また、元素分析、マススペクトルおよびＩＲスペクトル
の結果は、次の通りであった。Melting point: 127-129°C The results of elemental analysis, mass spectrum, and IR spectrum were as follows.
元素分析値 ＣＨＮ
計算値Ｃ％） ６８．３３ ３．９１ ４．９
８分析値ｃ％＞ ６９．１９ ３．９７ ５．
０６ＭＳ（ＥＴ）： ２８１（”）
Ｉ Ｒ（ＫＢｒ ｃｍ−’）： １２００．１２１０
（エーテル結合）１７００（カルボニル基）
３４５０（水酸基）
実施例２
攪拌器、温度計およびディーンスターク共沸蒸留トラッ
プを装着した反応器に無水マレイン酸３０ ｇ （０，
３モル）、トルエン２４０ｇを装入し、攪拌下で３−ヒ
ドロキシ−４゛−アミノジフェニルエーテル５０．３
ｇ （０，２５モル）を加え、反応を１時間行った０次
いで、Ｐ−）ルエンスルホン酸１．３ｇおよびＮ、Ｎ−
ジメチルアセトアミド８０ｇを加え、還流温度まで加熱
し、７時間反応を行った０反応終了後、実施例１と同様
な後処理を行い、目的の４＝（３−ヒドロキシフェノキ
シ）フェニルマレイミド６４．３ｇ （収率９１．５
％）を得た。Elemental analysis value CHN Calculated value C%) 68.33 3.91 4.9
8 analysis value c%> 69.19 3.97 5.
06MS (ET): 281 ('') I R (KBr cm-'): 1200.1210
(ether bond) 1700 (carbonyl group) 3450 (hydroxyl group) Example 2 30 g of maleic anhydride (0,
3 mol), 240 g of toluene was charged, and 50.3 g of 3-hydroxy-4'-aminodiphenyl ether was added under stirring.
g (0.25 mol) was added and the reaction was carried out for 1 hour. Then 1.3 g of P-)luenesulfonic acid and N,N-
80 g of dimethylacetamide was added, heated to reflux temperature, and reacted for 7 hours. After completion of the reaction, the same post-treatment as in Example 1 was carried out to obtain 64.3 g of the desired 4=(3-hydroxyphenoxy)phenylmaleimide ( Yield 91.5
%) was obtained.
純度分析の結果は、純度９８．８％であった。The purity analysis result was 98.8% purity.
実施例３
攪拌器、温度計およびディーンスターク共沸蒸留トラッ
プを装着した反応器に無水マレイン酸６０ ｇ （０
，６１七ノリ、トルエン４８０ ｇおよびメタンスルホ
ン酸２．６ｇを装入し、攪拌下で還流温度まで加熱し、
予めＮ−メチル−２−ピロリドン１６０ｇに４−ヒドロ
キシ−４″−アミノジフェニルエーテル１００．５ ｇ
（０，５モル）を溶解した溶液を滴下コートにより５
時間で滴下し、同温度で５時間反応を行った０反応終了
後、実施例１と同様に後処理を行い、４−（４−ヒドロ
キシフェノキシ）フェニルマレイミドの黄色結晶１２９
ｇ（収率９２％）を得た。Example 3 60 g maleic anhydride (0
, 61 seven paste, 480 g of toluene and 2.6 g of methanesulfonic acid were charged, and heated to reflux temperature under stirring,
Add 100.5 g of 4-hydroxy-4″-aminodiphenyl ether to 160 g of N-methyl-2-pyrrolidone in advance.
(0.5 mol) was added by drop coating.
After the completion of the reaction, the yellow crystals of 4-(4-hydroxyphenoxy)phenylmaleimide 129
g (yield 92%) was obtained.
純度分析結果は、純度９９．０％であった。The purity analysis result was 99.0% purity.
融点１４７〜１４９℃
また、元素分析、マススペクトルおよびＩＲスペクトル
の結果は、次の通りであった。Melting point: 147-149° C. The results of elemental analysis, mass spectrum, and IR spectrum were as follows.
元素分析値 ＣＨＮ
計算値（％） ６８．３３ ３．９１ ４．９
８分析値（％） ６９．００ ４．０１ ５．
０８Ｍ５ （Ｅ Ｔ ） ： ２８１（”）Ｉ Ｒ（
ＫＢｒ Ｃ１−’）： １２３０（エーテル結合）１７
００（カルボニル基）
３４５０ （水酸基）
実施例４
溶剤にクロルヘンゼン４８０ｇを用いた以外は、実施例
３と同様な操作を行い、４−（４〜ヒドロキシフエノキ
シ）フェニルマレイミド１２５ｇ （収率８９％）を
得た。Elemental analysis value CHN Calculated value (%) 68.33 3.91 4.9
8 Analysis value (%) 69.00 4.01 5.
08M5 (ET): 281(”)I R(
KBr C1-'): 1230 (ether bond) 17
00 (carbonyl group) 3450 (hydroxyl group) Example 4 The same operation as in Example 3 was performed except that 480 g of chlorhenzene was used as the solvent, and 125 g of 4-(4-hydroxyphenoxy)phenylmaleimide (yield 89%) ) was obtained.
純度分析結果は、純度９９，２％であった。The purity analysis result was 99.2% purity.
特許出願人 三井東圧化学株式会社Patent applicant: Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
キシ〕フェニルマレイミド。 ２）３−（または４−）ヒドロキシ−４’−アミノジフ
ェニルエーテルと無水マレイン酸を水と共沸可能な有機
溶剤中、酸触媒の存在下で脱水閉環反応させることを特
徴とする４−〔３−（または４−）ヒドロキシフェノキ
シ〕フェニルマレイミドの製造方法。[Claims] 1) 4-[3- (or 4-) hydroxyphenoxy] phenylmaleimide represented by the general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I). 2) 4-[3] characterized by subjecting 3-(or 4-)hydroxy-4'-aminodiphenyl ether and maleic anhydride to a dehydration ring-closing reaction in the presence of an acid catalyst in an organic solvent capable of azeotroping with water. A method for producing -(or 4-)hydroxyphenoxy]phenylmaleimide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2154017A JP2951696B2 (en) | 1990-06-14 | 1990-06-14 | 4- (Hydroxyphenoxy) phenylmaleimide and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2154017A JP2951696B2 (en) | 1990-06-14 | 1990-06-14 | 4- (Hydroxyphenoxy) phenylmaleimide and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0446155A true JPH0446155A (en) | 1992-02-17 |
| JP2951696B2 JP2951696B2 (en) | 1999-09-20 |
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ID=15575089
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|---|---|---|---|
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005110984A1 (en) * | 2004-05-17 | 2005-11-24 | Daicel Chemical Industries, Ltd. | Process for producing cyclic n-hydroxyimide compound |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100509151C (en) * | 2005-12-31 | 2009-07-08 | 渤海大学 | Application of load type catalyst in synthesizing N phenyl maleimide |
-
1990
- 1990-06-14 JP JP2154017A patent/JP2951696B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005110984A1 (en) * | 2004-05-17 | 2005-11-24 | Daicel Chemical Industries, Ltd. | Process for producing cyclic n-hydroxyimide compound |
| JPWO2005110984A1 (en) * | 2004-05-17 | 2008-03-21 | ダイセル化学工業株式会社 | Method for producing N-hydroxy cyclic imide compound |
| US7582774B2 (en) | 2004-05-17 | 2009-09-01 | Daicel Chemical Industries, Ltd. | Process for producing cyclic N-hydroxy imide compounds |
| JP4690314B2 (en) * | 2004-05-17 | 2011-06-01 | ダイセル化学工業株式会社 | Method for producing N-hydroxy cyclic imide compound |
| US8217182B2 (en) | 2004-05-17 | 2012-07-10 | Daicel Chemical Industries, Ltd. | Process for producing cyclic N-hydroxy imide compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2951696B2 (en) | 1999-09-20 |
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