JPH0586778B2 - - Google Patents
Info
- Publication number
- JPH0586778B2 JPH0586778B2 JP21365485A JP21365485A JPH0586778B2 JP H0586778 B2 JPH0586778 B2 JP H0586778B2 JP 21365485 A JP21365485 A JP 21365485A JP 21365485 A JP21365485 A JP 21365485A JP H0586778 B2 JPH0586778 B2 JP H0586778B2
- Authority
- JP
- Japan
- Prior art keywords
- maleimide resin
- maleic anhydride
- maleimide
- reaction
- curability
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000008065 acid anhydrides Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 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 1
- 239000002648 laminated material Substances 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
- 239000000155 melt Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Pyrrole Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
〔産業上の利用分野〕
本発明は、硬化性、作業性が良好で耐熱性およ
び経済性に優れたマレイミド樹脂の製造方法に関
するものである。
〔従来技術〕
従来、ビスマレイミドを含め、マレイミド樹脂
は、一般に有機溶媒中で無水マレイン酸と芳香族
ポリアミンとを低温で反応させ、マレアミツク酸
とし、これに無水酢酸などの脱水剤と、酢酸ナト
リウムなどの脱水触媒とを加え、比較的低温で、
マレイミド化し、脱溶媒、再結晶、再沈澱などの
非常に工数のかかる後処理工程を経てつくられて
いる。更に使用した溶剤、脱水剤などの後処理に
も多大の経費を要するため、非常に高価なものと
なつている。
このようにして得られる２段法のマレイミド樹
脂は、耐熱性は優れているが一般に、硬化性が劣
り、成形温度を高くしたり、ポストキユアーに多
大なエネルギーを要したり、エポキシ樹脂などの
併用により、耐熱性をある程度犠牲にして、硬化
性を改善するなどの工夫がなされている。
これに対し、無水マレイン酸とアミン類とを無
溶媒、無触媒で高温下、付加反応と縮合反応とを
同時におこなわせてマレイミドを得ようとする１
段法の試みも古くからおこなわれていたが、マレ
イミドの収率が悪く、分子間の縮合反応が起つて
ゲル化し易いため、実用には至らなかつた。
〔発明の目的〕
本発明は、従来１段法ではできなかつた高収率
のマレイミド樹脂を得んとして研究した結果、脱
水剤およびゲル化防止剤として過剰の無水マレイ
ン酸を使用することにより、作業性の良い高収率
のマレイミド樹脂が得られるとの知見を得、更に
この知見に基づき種々研究を進めて、本発明を完
成するに至つたものである。その目的とするとこ
ろは、作業性、硬化性が良好でガラス転移温度が
高く、低熱膨脹で、耐熱性および経済性に優れた
マレイミド樹脂の製造方法を提供するにある。
〔発明の構成〕
本発明は、無水マレイン酸の融解液に酸無水物
環に対するNH2基の当量比0.3〜0.9の範囲で芳香
族ポリアミンを徐々に添加し、130〜200℃で760
〜200mmHgの圧力下で反応させ、反応後、熱水で
未反応物を抽出除去することを特徴とするマレイ
ミド樹脂の製造方法である。
本発明において用いられる芳香族ポリアミンと
しては、例えばｍ−またはｐ−フエニレンジアミ
ン，４，′４−ジアミノジフエニルメタン、３，
3′−ジメチル−４，4′−ジアミノジフエニルメタ
ン、３，3′−ジエチル−４，4′−ジアミノジフエ
ニルメタン、２，２−ビス（４−アミノフエニ
ル）プロパン、４，4′−ジアミノジフエニルエー
テル、４，4′−ジアミノジフエニルスルホン、ｍ
−またはｐ−キシリレンジアミン、また、平均組
成が一般式
[Industrial Field of Application] The present invention relates to a method for producing a maleimide resin that has good curability and workability, excellent heat resistance and economical efficiency. [Prior Art] Conventionally, maleimide resins, including bismaleimide, are generally produced by reacting maleic anhydride and aromatic polyamine in an organic solvent at low temperatures to obtain maleamic acid, which is then treated with a dehydrating agent such as acetic anhydride and sodium acetate. by adding a dehydration catalyst such as
It is made by converting it into maleimide and going through a very time-consuming post-processing process such as desolvation, recrystallization, and reprecipitation. Furthermore, the post-treatment of the used solvent, dehydrating agent, etc. also requires a great deal of expense, making it very expensive. The maleimide resin obtained by the two-step process has excellent heat resistance, but generally has poor curability, requiring high molding temperatures, a large amount of energy for post-curing, and the use of epoxy resins etc. Therefore, efforts have been made to improve curability by sacrificing heat resistance to some extent. On the other hand, attempts have been made to obtain maleimide by simultaneously carrying out an addition reaction and a condensation reaction between maleic anhydride and amines in the absence of solvents and catalysts at high temperatures.
Attempts have been made to use the step method for a long time, but the yield of maleimide was poor and gelation easily occurred due to intermolecular condensation reactions, so it was not put to practical use. [Object of the Invention] The present invention was developed as a result of research aimed at obtaining a high yield of maleimide resin, which could not be achieved by a conventional one-stage method. We found that a maleimide resin with good workability and high yield can be obtained, and based on this knowledge, we conducted various studies and completed the present invention. The object is to provide a method for producing a maleimide resin which has good workability and curability, a high glass transition temperature, low thermal expansion, excellent heat resistance and economical efficiency. [Structure of the Invention] The present invention involves gradually adding an aromatic polyamine to a melt of maleic anhydride at an equivalent ratio of NH 2 groups to acid anhydride rings in the range of 0.3 to 0.9, and
This is a method for producing a maleimide resin, which is characterized by reacting under a pressure of ~200 mmHg and, after the reaction, extracting and removing unreacted substances with hot water. Examples of aromatic polyamines used in the present invention include m- or p-phenylenediamine, 4,'4-diaminodiphenylmethane, 3,
3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diamino Diphenyl ether, 4,4'-diaminodiphenyl sulfone, m
- or p-xylylenediamine, and also has an average composition of the general formula
本発明方法に従うと、無水マレイン酸と芳香族
ポリアミンとから無溶媒、無触媒で、高収率のマ
レイミド樹脂を得ることができ、経済性に優れて
いる。得られた樹脂は、低融点で、アセトン、メ
チルエチルケトン、テトラヒドロフラン、ジオキ
サンなどの低沸点溶媒に対する溶解性も良く、硬
化性は非常に良好で耐熱性にも優れているので成
形材料、粉体塗料、積層材料、接着剤などの用途
に好適である。
〔実施例〕
実施例 １〜４
無水マレイン酸を融解し、これに芳香族ポリア
ミンを第１表に示すように種類と量を変えて、該
ポリアミンを徐々に添加し、添加後、400〜500mm
Hgの減圧下で反応し、脱水した。反応後、トル
エン25ｇと熱水200ｇを加え、還流させながら、
５分間撹拌混合した。静置すると抽出水が上層に
分離する。これを吸引除去し、更に熱水200ｇを
２回加え、同様に洗浄をくり返した。その後、残
存水分とトルエンを減圧留去してマレイミド樹脂
を得た。
比較例 １
実施例２のNH2基／酸無水物環の比を１にし
て、同様の反応をおこなつた。しかし、４，4′−
ジアミノジフエニルメタンの添加終了と同時にゲ
ル化した。
比較例 ２
無水マレイン酸と４，4′−ジアミノジフエニル
メタンとから常法（２段法）により、ビスマレイ
ミドを得た。
各例の特性値を第１表に示した。
実施例１〜４は比較例２に比べ融点が低くて作
業し易い。実施例２のマレイミド樹脂の赤外線吸
収スペクトルを図１に示したが、比較例２とほと
んど一致し、高純度である。
硬化性は、比較例２に比べ、大巾に短縮され、
ガラス転移温度（Tg）にほぼ同じである。
According to the method of the present invention, a maleimide resin can be obtained in high yield from maleic anhydride and an aromatic polyamine without a solvent or catalyst, and is excellent in economic efficiency. The resulting resin has a low melting point, good solubility in low boiling point solvents such as acetone, methyl ethyl ketone, tetrahydrofuran, and dioxane, very good curability, and excellent heat resistance, so it can be used as a molding material, powder coating, etc. Suitable for applications such as laminated materials and adhesives. [Example] Examples 1 to 4 Maleic anhydride is melted, and aromatic polyamines are gradually added thereto in different types and amounts as shown in Table 1.
The mixture was reacted under reduced pressure of Hg and dehydrated. After the reaction, add 25g of toluene and 200g of hot water, and while refluxing,
The mixture was stirred and mixed for 5 minutes. When left to stand still, the extracted water separates into an upper layer. This was removed by suction, 200 g of hot water was added twice, and the washing was repeated in the same manner. Thereafter, residual moisture and toluene were distilled off under reduced pressure to obtain a maleimide resin. Comparative Example 1 The same reaction as in Example 2 was carried out except that the ratio of NH 2 group/acid anhydride ring was set to 1. However, 4,4′−
Gelation occurred at the same time as the addition of diaminodiphenylmethane was completed. Comparative Example 2 Bismaleimide was obtained from maleic anhydride and 4,4'-diaminodiphenylmethane by a conventional method (two-step method). The characteristic values of each example are shown in Table 1. Examples 1 to 4 have lower melting points than Comparative Example 2 and are easier to work with. The infrared absorption spectrum of the maleimide resin of Example 2 is shown in FIG. 1, and it almost matches that of Comparative Example 2, indicating high purity. The curability was significantly shortened compared to Comparative Example 2,
It is almost the same as the glass transition temperature (Tg).
第１図は、実施例２で得たマレイミド樹脂の赤
外線吸収スペクトルである。
FIG. 1 is an infrared absorption spectrum of the maleimide resin obtained in Example 2.
Claims (1)
るNH2基の当量比0.3〜0.9の範囲で、芳香族ポリ
アミンを徐々に添加し、130〜200℃で760〜200mm
Hgの圧力下で反応させ、反応後熱水で、未反応
物を抽出除去することを特徴とするマレイミド樹
脂の製造方法。1 Gradually add an aromatic polyamine to a molten solution of maleic anhydride at an equivalent ratio of NH 2 groups to the acid anhydride ring in the range of 0.3 to 0.9, and heat to 760 to 200 mm at 130 to 200 °C.
A method for producing maleimide resin, which comprises reacting under the pressure of Hg and extracting and removing unreacted substances with hot water after the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21365485A JPS6277363A (en) | 1985-09-28 | 1985-09-28 | Production of maleimide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21365485A JPS6277363A (en) | 1985-09-28 | 1985-09-28 | Production of maleimide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6277363A JPS6277363A (en) | 1987-04-09 |
| JPH0586778B2 true JPH0586778B2 (en) | 1993-12-14 |
Family
ID=16642742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21365485A Granted JPS6277363A (en) | 1985-09-28 | 1985-09-28 | Production of maleimide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6277363A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017066132A (en) * | 2015-09-29 | 2017-04-06 | ユニチカ株式会社 | Process for producing maleimide |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02274731A (en) * | 1989-04-17 | 1990-11-08 | Sumitomo Bakelite Co Ltd | Production of amine-modified maleimide resin |
| JP2519474Y2 (en) * | 1991-03-30 | 1996-12-04 | ミドリ安全工業株式会社 | Air cleaner |
| JPH06117400A (en) * | 1992-02-25 | 1994-04-26 | Asahi Kogyosha:Kk | Air blower unit with filter |
| JP4491898B2 (en) * | 2000-03-15 | 2010-06-30 | 住友ベークライト株式会社 | Maleimide resin and process for producing the same |
| JP2020125275A (en) * | 2019-02-06 | 2020-08-20 | ユニチカ株式会社 | Method of producing maleimide |
| JP7464474B2 (en) * | 2020-07-29 | 2024-04-09 | 日本化薬株式会社 | Maleimide resin, curable resin composition and cured product thereof |
-
1985
- 1985-09-28 JP JP21365485A patent/JPS6277363A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017066132A (en) * | 2015-09-29 | 2017-04-06 | ユニチカ株式会社 | Process for producing maleimide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6277363A (en) | 1987-04-09 |
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