JP3587404B2 - Method for producing maleimide resin - Google Patents
Method for producing maleimide resin Download PDFInfo
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- JP3587404B2 JP3587404B2 JP33902195A JP33902195A JP3587404B2 JP 3587404 B2 JP3587404 B2 JP 3587404B2 JP 33902195 A JP33902195 A JP 33902195A JP 33902195 A JP33902195 A JP 33902195A JP 3587404 B2 JP3587404 B2 JP 3587404B2
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- Prior art keywords
- salt
- diamine
- resin
- methanol
- maleic acid
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- 229920005989 resin Polymers 0.000 title claims description 25
- 239000011347 resin Substances 0.000 title claims description 25
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 150000003839 salts Chemical class 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 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
- 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 5
- -1 allyl compound Chemical class 0.000 description 5
- 229920003192 poly(bis maleimide) Polymers 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- PADSMSXOUQYFSZ-UHFFFAOYSA-N 1-[(2,5-dioxopyrrol-1-yl)-diphenylmethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)N1C(=O)C=CC1=O PADSMSXOUQYFSZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- HLPKYOCVWVMBMR-UHFFFAOYSA-N azane benzylbenzene Chemical compound N.N.C=1C=CC=CC=1CC1=CC=CC=C1 HLPKYOCVWVMBMR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は耐熱性、機械的強度、加工性に優れるマレイミド系樹脂の製造方法に関するものである。
【０００２】
【従来の技術】
従来のマレイミド樹脂はマレイン酸無水物と芳香族ジアミンを反応し、マレアミド酸とした後、閉環反応によりビスマレイミドを得ている。
しかし、中間体であるマレアミド酸は溶解性が悪く、また、マレアミド酸の分子間脱水によるアミド化副反応によるゲル化などを防ぐために、大量の溶剤中で反応せざるを得ない欠点があった。
このためマレイミド樹脂は、優れた特性を持ちながらも製造上の制約があった。
更に、ビスマレイミド樹脂単独の硬化物は非常に脆いので単独では使用に耐えず、ジアミン、アリル化合物等の可とう性を具備する変性剤により変性した場合でも完全に脆さを改善するには至っていない。
【０００３】
【発明が解決しようとする課題】
本発明が解決しようとする課題は強靱性、耐熱性に優れ、かつ製造上の制約のないマレイミド系樹脂を製造する方法を見いだすことにある。
【０００４】
【課題を解決するための手段】
本発明は、上記の課題を解決するため鋭意検討した結果、
マレイン酸とジアミンとからなる塩で、その塩が、
ａ）メタノール単独溶媒、
ｂ）メタノールと、エタノール以上の高級アルコール又は／及び芳香族炭化水素の混合溶媒、又は、
ｃ）メタノール・水・芳香族炭化水素３成分系混合溶媒中で合成されるものであり、
マレイン酸とジアミンとのモル比が２：１又は１：１である塩、あるいはモル比が２：１の塩と１：１の塩との混合物を１００〜１８０℃で加熱して得られることを特徴とするマレイミド系樹脂の製造方法を見い出したものである。
【０００５】
【発明の実施の形態】
本発明では樹脂の中間体として通常使われているアミック酸を経由せず、マレイン酸−ジアミン塩を中間体として製造を行う。
本発明におけるジアミンとしては、ジアミノジフェニルメタン、ジアミノジフェニルエーテル、ジアミノジフェニルスルホン、フェニレンジアミンなど通常のマレイミド合成に使われるものはすべて使用できる。
また、複数の種類の芳香族アミンを併用することも可能である。
【０００６】
マレイン酸−ジアミン塩中間体は、マレイン酸の溶液中に芳香族アミンの溶液を滴下することにより沈殿した生成物を乾燥し得られる。
マレイン酸−ジアミン塩の組成は、塩を生成する溶媒及び反応モル比によって変化させる。
マレイン酸−ジアミノジフェニルメタン塩の場合、メタノール中で得られる塩は１：１塩が主生成となり、メタノール・水・トルエン３成分系混合溶媒中では２：１塩が主生成となる。
メタノールとエタノール以上の高級アルコール又は／及び芳香族炭化水素の混合溶媒を用いた場合、１：１塩と２：１塩の混合物が生成し、高級アルコール、芳香族炭化水素のメタノールに対する添加量によって混合比を変えることができる。
【０００７】
得られたマレイン酸−ジアミン塩中間体を乾燥機中、または、押し出し機等の混練機中で１００〜１８０℃に加熱する事により、脱水と共にマレイミド化反応が起こり樹脂が得られる。加熱時間は１２０℃で数時間、１８０℃で１０分程度で反応が終了する。反応時間はイミド化による縮合水の発生がなくなるよう決定される。
温度が１００℃未満では反応速度が急激に低下し、未反応物の残存が起こり高分子量の樹脂が得られない。１００℃から１２０℃のあいだは温度の微妙な変化でも単位時間あたりの反応率が大きく変化するので１２０℃以上が好ましい。
温度が１８０℃を越えると反応は非常に速いが、副反応による部分ゲル化が起こるため、軟化する樹脂が得られるものの溶剤に不溶な部分を含むものとなる。１００℃から１８０℃ではゲル化反応がほとんど起こることなくイミド化が起こるためＮ−メチルピロリドン、Ｎ，Ｎ−ジメチルホルムアミド等の溶剤に可溶な樹脂が得られる。
【０００８】
得られる樹脂は、従来のマレイミド樹脂と同様に、粉砕してレジンとして、溶剤に溶かしてワニスとして使用できる。
【０００９】
樹脂は更に加熱する事により硬化するが、ビスマレイミド単独硬化物や、ジアミン添加ビスマレイミド硬化物に比べ靱性のある硬化物が得られる。
硬化物の靱性は中間体塩の種類、混合比によって変化し、１：１塩の比率が高いほどより靱性を持つものとなる。
【００１０】
【実施例】
（実施例１）
マレイン酸１１６ｇ（１ｍｏｌ）をメタノール１７４ｇに溶解した溶液に、ジアミノジフェニルメタン１９８ｇ（１ｍｏｌ）をメタノール３９６ｇに溶解した溶液を３０分かけて滴下した。
生成した沈殿を濾過したのち、風乾してマレイン酸−ジアミノジフェニルメタン塩を得た。
この塩を１２０℃で４時間乾燥機中で加熱し、樹脂２５７ｇが得られた。
【００１１】
（実施例２）
マレイン酸１１６ｇ（１ｍｏｌ）をメタノール３４８ｇに溶解した溶液に、ジアミノジフェニルメタン９９ｇ（０．５ｍｏｌ）をメタノール４９．５ｇ・トルエン２９７ｇの混合溶媒に溶解した溶液を３０分かけて滴下した。
生成した沈殿を濾過したのち、風乾してマレイン酸−ジアミノジフェニルメタン塩を得た。
この塩を１４０℃で１時間乾燥機中で加熱し、樹脂１３９ｇが得られた。
【００１２】
（実施例３）
マレイン酸１１６ｇ（１ｍｏｌ）をメタノール１１６ｇ・２−プロパノール２３２ｇ混合溶媒に溶解した溶液に、ジアミノジフェニルメタン９９ｇ（０．５ｍｏｌ）をメタノール９９ｇに溶解した溶液を３０分かけて滴下した。
生成した沈殿を濾過したのち、風乾してマレイン酸−ジアミノジフェニルメタン塩を得た。
この塩を１２０℃で２時間乾燥機中で加熱し、樹脂１５８ｇが得られた。
【００１３】
（実施例４）
実施例１で得られた塩１ｇをＮ−メチル−２−ピロリドン２ｇに溶解し、５０φのアルミカップに入れ、乾燥機中１４０℃で１時間更に１８０℃で１〜８時間加熱した。
【００１４】
（実施例５）
実施例１で得られた樹脂１ｇをＮ−メチル−２−ピロリドン２ｇに溶解し、５０φのアルミカップに入れ、乾燥機中１４０℃で１時間更に１８０℃で１〜８時間加熱した。
【００１５】
（比較例１）
ビスマレイミドジフェニルメタン／ジアミノジフェニルメタンの等モル混合物１ｇをＮ−メチル−２−ピロリドン２ｇに溶解して、５０φのアルミカップに入れ、乾燥機中１４０℃で１時間更に１８０℃で１〜８時間加熱した。
【００１６】
【表１】
【発明の効果】
本方法の優れた点は、扱いやすく精製し易い塩を中間体として用い、樹脂化段階では溶剤を用いないか、少量の溶剤を用いるだけでゲル化することなく樹脂を得られ、また、得られる樹脂は従来のビスマレイミド硬化物に比べ靱性を持つ点にある。
本方法を用いることにより耐熱性、強靱性が高く、製造上の制約のないマレイミド系樹脂を製造することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a maleimide resin having excellent heat resistance, mechanical strength, and processability.
[0002]
[Prior art]
A conventional maleimide resin reacts maleic anhydride with an aromatic diamine to produce maleamic acid, and then obtains bismaleimide by a ring closure reaction.
However, the maleamic acid, which is an intermediate, has poor solubility, and has the disadvantage that it must be reacted in a large amount of solvent to prevent gelation due to amidation side reaction due to intermolecular dehydration of maleamic acid. .
For this reason, the maleimide resin has limitations in production, while having excellent properties.
Furthermore, the cured product of the bismaleimide resin alone is very brittle and cannot be used alone, and even when modified with a flexible modifier such as a diamine or an allyl compound, it is possible to completely improve the brittleness. Not in.
[0003]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to find a method for producing a maleimide resin having excellent toughness and heat resistance and having no restrictions on production.
[0004]
[Means for Solving the Problems]
The present invention has been made as a result of intensive studies to solve the above problems,
A salt consisting of maleic acid and a diamine,
a) methanol alone solvent,
b) a mixed solvent of methanol and a higher alcohol or / and aromatic hydrocarbon higher than ethanol, or
c) synthesized in a ternary mixed solvent of methanol, water and aromatic hydrocarbon,
A salt obtained by heating a salt having a molar ratio of maleic acid and diamine of 2: 1 or 1: 1 or a mixture of a salt having a molar ratio of 2: 1 and a salt of 1: 1 at 100 to 180 ° C. A method for producing a maleimide resin characterized by the following.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, the production is carried out using a maleic acid-diamine salt as an intermediate without passing through an amic acid which is usually used as an intermediate of a resin.
As the diamine in the present invention, any of diamine diphenylmethane, diamino diphenyl ether, diamino diphenyl sulfone, phenylenediamine and the like used in ordinary maleimide synthesis can be used.
It is also possible to use a plurality of types of aromatic amines in combination.
[0006]
The maleic acid-diamine salt intermediate is obtained by drying a precipitated product by dropping a solution of an aromatic amine into a solution of maleic acid.
The composition of the maleic acid-diamine salt varies depending on the solvent for forming the salt and the molar ratio of the reaction.
In the case of maleic acid-diaminodiphenylmethane salt, a 1: 1 salt is mainly produced as a salt obtained in methanol, and a 2: 1 salt is mainly produced in a ternary mixed solvent of methanol, water and toluene.
When a mixed solvent of methanol and ethanol or higher alcohol or / and aromatic hydrocarbon is used, a mixture of 1: 1 salt and 2: 1 salt is formed, and depending on the addition amount of higher alcohol and aromatic hydrocarbon to methanol. The mixing ratio can be changed.
[0007]
By heating the obtained maleic acid-diamine salt intermediate in a dryer or a kneader such as an extruder to 100 to 180 ° C., a maleimidation reaction occurs together with dehydration to obtain a resin. The heating is completed at 120 ° C. for several hours and at 180 ° C. for about 10 minutes. The reaction time is determined so that condensed water is not generated by imidation.
When the temperature is lower than 100 ° C., the reaction rate is sharply reduced, and unreacted substances remain, so that a high molecular weight resin cannot be obtained. Between 100 ° C. and 120 ° C., the reaction rate per unit time greatly changes even with a slight change in temperature, so that it is preferably 120 ° C. or more.
When the temperature exceeds 180 ° C., the reaction is very fast, but partial gelation occurs due to a side reaction, so that a softening resin is obtained but contains a portion insoluble in a solvent. At a temperature of 100 ° C. to 180 ° C., imidization occurs almost without causing a gelling reaction, so that a resin soluble in a solvent such as N-methylpyrrolidone, N, N-dimethylformamide is obtained.
[0008]
The obtained resin can be pulverized and used as a resin, or dissolved in a solvent and used as a varnish, similarly to a conventional maleimide resin.
[0009]
The resin is cured by further heating, but a cured product having toughness compared to a bismaleimide alone cured product or a diamine-added bismaleimide cured product is obtained.
The toughness of the cured product varies depending on the type and mixing ratio of the intermediate salt, and the higher the ratio of 1: 1 salt, the more toughness.
[0010]
【Example】
(Example 1)
A solution in which 198 g (1 mol) of diaminodiphenylmethane was dissolved in 396 g of methanol was added dropwise to a solution of 116 g (1 mol) of maleic acid in 174 g of methanol over 30 minutes.
The resulting precipitate was filtered and air-dried to obtain maleic acid-diaminodiphenylmethane salt.
This salt was heated in a dryer at 120 ° C. for 4 hours to obtain 257 g of a resin.
[0011]
(Example 2)
A solution in which 99 g (0.5 mol) of diaminodiphenylmethane was dissolved in a mixed solvent of 49.5 g of methanol and 297 g of toluene was added dropwise to a solution of 116 g (1 mol) of maleic acid dissolved in 348 g of methanol over 30 minutes.
The resulting precipitate was filtered and air-dried to obtain maleic acid-diaminodiphenylmethane salt.
This salt was heated in a drier at 140 ° C. for 1 hour to obtain 139 g of a resin.
[0012]
(Example 3)
To a solution of 116 g (1 mol) of maleic acid dissolved in a mixed solvent of 116 g of methanol and 232 g of 2-propanol, a solution of 99 g (0.5 mol) of diaminodiphenylmethane dissolved in 99 g of methanol was added dropwise over 30 minutes.
The resulting precipitate was filtered and air-dried to obtain maleic acid-diaminodiphenylmethane salt.
This salt was heated in a dryer at 120 ° C. for 2 hours to obtain 158 g of a resin.
[0013]
(Example 4)
1 g of the salt obtained in Example 1 was dissolved in 2 g of N-methyl-2-pyrrolidone, placed in a 50φ aluminum cup, and heated in a dryer at 140 ° C. for 1 hour and further at 180 ° C. for 1 to 8 hours.
[0014]
(Example 5)
1 g of the resin obtained in Example 1 was dissolved in 2 g of N-methyl-2-pyrrolidone, placed in a 50φ aluminum cup, and heated in a dryer at 140 ° C. for 1 hour and further at 180 ° C. for 1 to 8 hours.
[0015]
(Comparative Example 1)
1 g of an equimolar mixture of bismaleimidodiphenylmethane / diaminodiphenylmethane was dissolved in 2 g of N-methyl-2-pyrrolidone, placed in a 50φ aluminum cup, and further heated at 140 ° C. for 1 hour in a dryer and further at 180 ° C. for 1 to 8 hours. .
[0016]
[Table 1]
【The invention's effect】
The advantage of this method is that it uses a salt that is easy to handle and purify as an intermediate, does not use a solvent in the resination step, or obtains a resin without gelling by using only a small amount of solvent. The resin obtained has toughness as compared with a conventional bismaleimide cured product.
By using this method, a maleimide-based resin having high heat resistance and toughness and having no restrictions in production can be produced.
Claims (2)
ａ）メタノール単独溶媒、
ｂ）メタノールと、エタノール以上の高級アルコール又は／及び芳香族炭化水素の混合溶媒、又は、
ｃ）メタノール・水・芳香族炭化水素３成分系混合溶媒中で合成されるものであり、
マレイン酸とジアミンとのモル比が２：１又は１：１である塩、あるいはモル比が２：１の塩と１：１の塩との混合物を１００〜１８０℃で加熱して得られることを特徴とするマレイミド系樹脂の製造方法。A salt consisting of maleic acid and a diamine,
a) methanol alone solvent,
b) a mixed solvent of methanol and a higher alcohol or / and aromatic hydrocarbon higher than ethanol, or
c) synthesized in a ternary mixed solvent of methanol, water and aromatic hydrocarbon,
A salt obtained by heating a salt having a molar ratio of maleic acid and diamine of 2: 1 or 1: 1 or a mixture of a salt having a molar ratio of 2: 1 and a salt of 1: 1 at 100 to 180 ° C. A method for producing a maleimide-based resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33902195A JP3587404B2 (en) | 1995-12-26 | 1995-12-26 | Method for producing maleimide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33902195A JP3587404B2 (en) | 1995-12-26 | 1995-12-26 | Method for producing maleimide resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09176241A JPH09176241A (en) | 1997-07-08 |
| JP3587404B2 true JP3587404B2 (en) | 2004-11-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33902195A Expired - Fee Related JP3587404B2 (en) | 1995-12-26 | 1995-12-26 | Method for producing maleimide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3587404B2 (en) |
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1995
- 1995-12-26 JP JP33902195A patent/JP3587404B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09176241A (en) | 1997-07-08 |
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