JPH0643392B2 - Method for producing maleimide resin - Google Patents
Method for producing maleimide resinInfo
- Publication number
- JPH0643392B2 JPH0643392B2 JP6500685A JP6500685A JPH0643392B2 JP H0643392 B2 JPH0643392 B2 JP H0643392B2 JP 6500685 A JP6500685 A JP 6500685A JP 6500685 A JP6500685 A JP 6500685A JP H0643392 B2 JPH0643392 B2 JP H0643392B2
- Authority
- JP
- Japan
- Prior art keywords
- maleic anhydride
- maleimide resin
- reaction
- mmhg
- producing
- 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 title claims description 16
- 229920005989 resin Polymers 0.000 title claims description 15
- 239000011347 resin Substances 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229920000768 polyamine Polymers 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000008065 acid anhydrides Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000003949 imides Chemical group 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-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
- 239000003054 catalyst Substances 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 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
- 238000011160 research Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-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
- 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 239000002253 acid Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010030 laminating 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
- 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
- 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
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 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
Landscapes
- Pyrrole Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】 〔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。TECHNICAL FIELD The present invention relates to a method for producing a maleimide resin having excellent curability, workability, heat resistance, and economy.
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、マレアミック酸とし、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、再沈殿または、水洗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、水洗液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っている。Conventionally, maleimide resins, including bismaleimide, are generally reacted in an organic solvent with maleic anhydride and an aromatic polyamine at low temperature to form maleamic acid, which is then dehydrated with acetic anhydride and dehydrated with sodium acetate. It is prepared by adding a catalyst and maleimidating at a relatively low temperature, and performing a very time-consuming post-treatment process such as desolvation, recrystallization, reprecipitation, or washing with water. Further, the post-treatment of the used solvent, dehydrating agent, washing solution, etc. requires a great deal of cost, and is therefore very expensive.
このようにして得られた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、ポストキュアーに多大のエネルギーを要し
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。The two-stage maleimide resin thus obtained is excellent in heat resistance, but is generally inferior in curability, requires a high molding temperature, requires a large amount of energy for post cure, and has an epoxy resin. In combination with, the heat resistance is sacrificed to some extent, and the curability is improved.
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って、ゲル化し易いため、実
用には至らなかった。On the other hand, maleic anhydride and amines, without solvent,
An attempt of a one-step method for obtaining a maleimide by simultaneously performing an addition reaction and a condensation reaction at a high temperature without a catalyst is also conducted.
Although it has been carried out for a long time, it has not been put to practical use because the yield of maleimide is poor and an intermolecular condensation reaction occurs to easily cause gelation.
本発明は、従来、１段法ではできなかった高純度・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、高純度・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った
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。The present invention aims to obtain a high-purity, high-yield maleimide resin that could not be conventionally obtained by the one-step method, and as a result of research, by using an excess of maleic anhydride as a dehydrating agent and an antigelling agent, The present invention has been completed by obtaining the knowledge that a maleimide resin with high workability and high purity and high yield can be obtained, and further conducting various researches based on this knowledge. It is an object of the invention to provide a method for producing a maleimide resin having good workability and curability, a high glass transition temperature, a low thermal expansion coefficient, and excellent heat resistance and economical efficiency.
〔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0.2〜0.8の範囲で、芳香族ポリアミン
を徐々に添加し、１３０〜２００℃で、７６０〜２００
mmHgの常圧または減圧下で反応させ、反応後、速やかに
１００mmHg以下に減圧し、過剰の無水マレイン酸を除去
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。[Structure of the Invention] The present invention is to gradually add an aromatic polyamine to a molten solution of maleic anhydride at an equivalence ratio of NH 2 groups to an acid anhydride ring of 0.2 to 0.8, and to obtain 760 at 130 to 200 ° C. ~ 200
It is a method for producing a maleimide resin, which comprises reacting at a normal pressure of mmHg or a reduced pressure, and immediately after the reaction, the pressure is reduced to 100 mmHg or less to remove excess maleic anhydride.
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−フェニレンジアミン、4,4′−
ジアミノジフェニルメタン、3,3′−ジメチル−4,4′−
ジアミノジフェニルメタン、3,3′−ジエチル−4,4′−
ジアミノジフェニルメタン、2,2−ビス（４−アミノフ
ェニル）プロパン、4,4′−ジアミノフェニルエーテ
ル、4,4′−ジアミノジフェニルスルホン、ｍ−または
ｐ−キシリレンジアミン、また、平均組成が一般式 で示されるポリアミンなどをあげることができる。As the aromatic polyamine used in the present invention,
For example, 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'-diaminophenyl ether, 4,4'-diaminodiphenyl sulfone, m- or p-xylylenediamine, and an average composition of general formula Examples thereof include polyamines and the like.
芳香族ポリアミンは、NH2基／酸無水物環の当量比が、
0.2〜0.8は、好ましくは、0.3〜0.7の範囲で用いるのが
よい。適度に過剰な無水マレイン酸は、脱水剤として作
用するとともに、溶剤および分子間縮合反応の抑制剤即
ち、ゲル化防止剤としても作用する。そのため、イミド
環成分の高純度・高収率に有効に作用する。The aromatic polyamine has an equivalent ratio of NH 2 group / acid anhydride ring of
0.2 to 0.8 is preferably used in the range of 0.3 to 0.7. An appropriate excess of maleic anhydride acts as a dehydrating agent, and also acts as a solvent and an inhibitor of intermolecular condensation reaction, that is, an anti-gelling agent. Therefore, it effectively acts on the high purity and high yield of the imide ring component.
ポリアミンが多過ぎると、分子間の縮合反応が増えて、
イミド環成分の収率が減るとともに、反応中、非常にゲ
ル化し易くなる。少な過ぎると、少量ではあるが、一
部、NH2基に、２個の無水マレイン酸が付加して、イミ
ド環成分の純度・収率を低減し、耐熱性を低下させると
ともに、酸無水物の回収および再生処理に、余計な工数
をかけることになって、得策でない。If there are too many polyamines, the number of condensation reactions between molecules will increase,
The yield of the imide ring component decreases, and it becomes very easy to gel during the reaction. If it is too small, a small amount of 2 maleic anhydride is partially added to the NH 2 group, which reduces the purity and yield of the imide ring component, lowers the heat resistance, and reduces the acid anhydride. It is not a good idea because it will require extra man-hours for the recovery and recycling process of.
反応は、無水マレイン酸を、１３０〜２００℃、好まし
くは、１４０〜１８０℃に加熱して、融解し、これに芳
香族ポリアミンを、急激な温度上昇をさけながら、徐々
に添加しておこなわれる。添加後、その温度で７６０〜
２００mmHgの常圧または減圧下で、好ましくは、７５０
〜３００mmHgの減圧下で、約２〜１２０分反応する。The reaction is carried out by heating maleic anhydride to 130 to 200 ° C., preferably 140 to 180 ° C. to melt it, and gradually adding an aromatic polyamine thereto while avoiding a rapid temperature rise. . After addition, at that temperature 760-
Under normal pressure or reduced pressure of 200 mmHg, preferably 750
The mixture is reacted under a reduced pressure of 300 mmHg for about 2 to 120 minutes.
反応温度が低過ぎると、付加物であるアミック酸がいつ
までも、不溶物のまゝ残り、分子内縮合によるイミド環
の生成を阻害する。高過ぎると、分子間縮合およびイミ
ド環の不飽和基へのアミンの付加も起って、反応中にゲ
ル化し易くなる。If the reaction temperature is too low, the amic acid as an adduct will remain as an insoluble matter forever and inhibit the formation of an imide ring by intramolecular condensation. If it is too high, intermolecular condensation and addition of amine to the unsaturated group of the imide ring also occur, and gelation easily occurs during the reaction.
過剰の無水マレイン酸は、縮合水と反応して、マレイン
酸になるが、上記の温度では再び水を放出して、無水マ
レイン酸が再生される。そのため、無水マレイン酸が留
出しない程度の減圧下で反応して、脱水するのが好まし
い。Excess maleic anhydride reacts with condensed water to form maleic acid, but at the above temperature, water is released again to regenerate maleic anhydride. Therefore, it is preferable to dehydrate by reacting under a reduced pressure such that maleic anhydride is not distilled.
反応後は、１００mmHg以下の減圧下で速やかに過剰の無
水マレイン酸を除去する。このようにして無溶媒、無触
媒で、高純度・高収率のマレイミド樹脂が得られ、回収
された無水マレイン酸は、再度反応に使用できる。After the reaction, excess maleic anhydride is promptly removed under reduced pressure of 100 mmHg or less. In this way, a high-purity, high-yield maleimide resin can be obtained without a solvent and without a catalyst, and the recovered maleic anhydride can be used again in the reaction.
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、高純度・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、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。According to the method of the present invention, a maleimide resin having a high purity and a high yield can be obtained from maleic anhydride and an aromatic polyamine without using a solvent, and is highly economical. The resin obtained has a low melting point, good solubility in solvents, excellent curability, and excellent heat resistance, so it can be used in applications such as molding materials, powder coatings, laminating materials, and adhesives. It is suitable.
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徐
々に添加し、添加後、４００〜５００mmHgの減圧下で反
応し、脱水した。反応後、３０mmHgで５分、更に、５mm
Hgで３０分、減圧して過剰の無水マレイン酸を留去し、
マレイミド樹脂を得た。Examples 1 to 4 Maleic anhydride was melted, aromatic polyamine was gradually added thereto, and after the addition, the mixture was reacted under a reduced pressure of 400 to 500 mmHg and dehydrated. After reaction, 5 minutes at 30mmHg, then 5mm
Hg for 30 minutes under reduced pressure to remove excess maleic anhydride,
A maleimide resin was obtained.
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
反応をおこなった。しかし、4,4′−ジアミノジフェニ
ルメタンの添加終了と同時にゲル化した。Comparative Example 1 The same reaction was carried out with the ratio of NH 2 group / acid anhydride ring of Example 2 being 1. However, gelation occurred at the same time as the addition of 4,4'-diaminodiphenylmethane was completed.
比較例２ 無水マレイン酸と4,4′−ジアミノジフェニルメタンと
から常法（２段法）により、ビスマレイミドを得た。Comparative Example 2 Bismaleimide was obtained from maleic anhydride and 4,4'-diaminodiphenylmethane by a conventional method (two-step method).
各例の特性値を表１に示した。The characteristic values of each example are shown in Table 1.
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。Examples 1 to 4 have a lower melting point than Comparative Example 2 and are easy to work with. The infrared absorption spectrum of the maleimide resin of Example 2 is shown in FIG. 1, which almost coincides with that of Comparative Example 2 and has a high purity.
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)はほぼ同じである。The curability is greatly shortened as compared with Comparative Example 2, and the glass transition temperature (Tg) is almost the same.
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)
対するNH2基の当量比0.2〜0.8の範囲で、芳香族ポリア
ミンを徐々に添加し、１３０〜２００℃で、７６０〜２
００mmHgの圧力下で反応させ、反応後速やかに１００mm
Hg以下に減圧し、過剰の無水マレイン酸を除去すること
を特徴とするマレイミド樹脂の製造方法。1. An aromatic polyamine is gradually added to a molten solution of maleic anhydride at an equivalent ratio of NH 2 groups to acid anhydride rings of 0.2 to 0.8, and at 130 to 200 ° C., 760 to 2
React under a pressure of 00 mmHg, 100 mm immediately after the reaction
A method for producing a maleimide resin, which comprises reducing the pressure to Hg or less to remove an excess of maleic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6500685A JPH0643392B2 (en) | 1985-03-30 | 1985-03-30 | Method for producing maleimide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6500685A JPH0643392B2 (en) | 1985-03-30 | 1985-03-30 | Method for producing maleimide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61225215A JPS61225215A (en) | 1986-10-07 |
| JPH0643392B2 true JPH0643392B2 (en) | 1994-06-08 |
Family
ID=13274470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6500685A Expired - Lifetime JPH0643392B2 (en) | 1985-03-30 | 1985-03-30 | Method for producing maleimide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643392B2 (en) |
Families Citing this family (3)
| 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 |
| 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
- 1985-03-30 JP JP6500685A patent/JPH0643392B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61225215A (en) | 1986-10-07 |
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