1335917 九、發明說明： 【發明所屬之技術韻域】 本發明係有關一種雙馬來醯亞胺化合物及其製法，尤 其是有關一種具有不對稱結構之雙馬來亞醯胺物及 其製法。 【先前技術】 聚醯亞胺化合物熱穩定性高且具有優異的絕緣性、機 械強度、及抗化學腐蝕性，常用於多種電子加工材料。 然而’但由於傳統醯亞胺分子中的對稱與高度結晶結 .構，使得大部分的醯亞胺化合物不易溶於低沸點有機溶 劑，而僅溶於高沸點非質子極性溶液劑，例如N_甲基一 吼洛酮燒酮、二甲基乙酸胺等等。由於該些高；弗點非質子 極性溶液劑不易移除，往往會殘存於加工材料成品中，大 幅降低產品的機械性質與耐熱性質。 另方面、由於醯亞胺化合物本身不易溶於低沸點有 •機溶液中，古文不易與其他化合物或聚合物搭配推合使用， 限制了醯亞胺化合物的應用。 =種具有優異溶解性之改質醯亞胺化合物，乃應運而 生’符合工業實務應用的殷切需求。 【發明内容】 鐘於上述問題’本發明之主要目的在於提供-種具有 優異溶解性之雙馬來醯亞胺化合物。 一 種具有優異耐熱性與難 本發明之另一目的，係提供一 燃性之雙馬來醯亞胺化合物。 110300 6 1335917 本發明之另—目的，係提供一種可用 學特性之雙馬來酿亞胺化合物。 、有政改善電化 為了達上述及其他目的，本發明福霞 所示含：芏脸“ 的不毛月揭路-種如式⑴ 本胺結構之雙馬來醯亞胺化合物1335917 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a bimaleimide compound and a process for the preparation thereof, and more particularly to a bismaleimide having an asymmetric structure and a process for the preparation thereof. [Prior Art] Polyimine compounds have high thermal stability and excellent insulating properties, mechanical strength, and chemical resistance, and are commonly used in various electronic processing materials. However, due to the symmetry and high crystal structure in the traditional quinone imine molecule, most of the quinone imine compounds are not easily soluble in low-boiling organic solvents, but only in high-boiling aprotic polar solutions, such as N_. Methyl oxaprofenone, dimethylacetic acid amine, and the like. Due to the high level, the aprotic polar solution is difficult to remove and tends to remain in the finished product, greatly reducing the mechanical and thermal properties of the product. On the other hand, since the quinone imine compound itself is not easily soluble in the low boiling point organic solution, the ancient text is not easy to be combined with other compounds or polymers, which limits the application of the quinone imine compound. = A modified bismuth imide compound with excellent solubility has emerged as a result of the demand for industrial practice. SUMMARY OF THE INVENTION The above object is to provide a bismaleimide compound having excellent solubility. An excellent object of the present invention is to provide a flammable bismaleimide compound. 110300 6 1335917 Another object of the present invention is to provide a bismaleimine compound having a usable property. In order to achieve the above and other purposes, the Fuxia of the present invention contains: the face of the face of the 不 月 - - - - - 种 种 种 种 种 种 种 种 种 种 种 种 本
:中’R為氰基。該化合物係利用二胺 中進行反應形成軸酸，再於催化劑存在之條件= 化脫水反應㈣成之產物。該含三苯 势程' 方“或簡化雙馬來醯亞胺之後續成膜與加工 ^。另-方面、該化合物亦具有良好的難燃性與耐孰 性，可用作為難燃劑或用於改質樹脂之耐燃特性。再者、、 5亥化合物之拉電子純，可應詩電子產品之加工’提高 電子材料之介電常數，並調整電化學特性。 【實施方式】 本毛明揭不帛含二笨胺結構之新賴雙馬來醯亞胺 化合物及其製法，該化合物具有式⑴所示之結構： 110300 7 1335917 丁基酮及乙酸乙酯；以及非質子高溫極性溶劑，例如二甲 基曱酿胺或二甲基乙酿胺。 通常，步驟（A)係於0至40°C之溫度範圍内進行反 應’較佳係於15至30°C之溫度範圍内進行反應；溫度過 南έ使中間產物酿胺酸產生閉J衷的現象，而無法在後續反 應中順利形成本發明之新穎雙馬來醯亞胺化合物；一般而 言、在常溫常壓之條件下進行該步驟（Α)之反應即可。 該步驟（Α)之反應時間並無特別限制，只要能形成中 間產物醯胺酸即可。一般而言，步驟（/〇之反應時間係介 於6至24小時，較佳係介於6至12小時。反應完成後， 利用過濾的方式分離出中間產物醯胺酸，經純化洗滌後， 即可進行步驟（Β)之脫水環化反應。: Medium 'R is a cyano group. This compound is a product obtained by reacting a diamine to form a shaft acid, and then in the presence of a catalyst = a dehydration reaction (IV). The triphenyl potential-containing "square" or simplified subsequent film formation and processing of the bismaleimine. In addition, the compound also has good flame retardancy and stagnation resistance, and can be used as a flame retardant or The flame-retardant properties of the modified resin. In addition, the 5 hai compound pulls the electron pure, can improve the dielectric constant of the electronic material and adjust the electrochemical characteristics in the processing of the poetry electronic product. [Embodiment] A novel bis-maleimide compound having a structure of the formula (1): 110300 7 1335917 butyl ketone and ethyl acetate; and an aprotic high-temperature polar solvent, for example, Dimethyl amide amine or dimethyl ethamine. Generally, step (A) is carried out in a temperature range of from 0 to 40 ° C. Preferably, the reaction is carried out at a temperature ranging from 15 to 30 ° C; When the temperature is too high, the intermediate product of the amino acid is closed, and the novel bismaleimide compound of the present invention cannot be formed smoothly in the subsequent reaction; generally, the condition is carried out under normal temperature and normal pressure. The reaction of the step (Α) can be. The reaction time of (Α) is not particularly limited as long as the intermediate product proline is formed. In general, the reaction time of the step (/〇 is 6 to 24 hours, preferably 6 to 12 hours). After the reaction is completed, the intermediate product proline is separated by filtration, and after purification and washing, the dehydration cyclization reaction of the step (Β) can be carried out.
本發明之方法中，該步驟（Β)之脫水環化反應係將步 騾=)所形成之醯胺酸溶於溶劑中，添加催化劑與脫水劑 進行脫水環化，形成本發明含三苯胺結構之雙馬來酿亞胺 化合物。催化劑的實例包括 '義（醋酸幻等驗性催 化劑；該脫水劑之實例包括，㈣_醋盖厨。. 該步驟（Β)之脫水環化反應通常係於70至1201之㈤ =件下進行，較㈣於f 小時，較佳約10至12小時，再以滴入冰水的 即可獲得本發明含三笨胺結構之雙馬來酿 亞胺新穎化合物。 本發明含 苯胺結構之雙馬來醯亞胺化 110300 1335917 =三苯Μ構之雙馬來酿亞胺聚合物。該料劑的實例 Γ·; ，雙異丁腈咖)、或過氧化二苯甲釀 =^^^70至靴，較佳係於❹⑽ ……、牛下進仃，加入甲醇即可終止反應，最後、辑 得含三苯胺結構之雙馬來酿亞⑯聚合&。w " ㈣實施例’進—步說明本發明之 特點與功效’但非用於限制本發明之範蜂。 實施例 實施例1 使用氮氣沖滌250毫升配有加料管之三頸圓底燒 瓶’之後、將2. 057克（20. 98毫莫耳）§來酸肝之丙綱溶 液(20宅升)加入該三頸圓底燒瓶；接著、經由加料管將 3.〇〇〇克（9.99^莫耳）4,4，_二胺基_4，’_氰基三苯胺之两In the method of the present invention, the dehydration cyclization reaction of the step (Β) dissolves the proline acid formed by the step =) in a solvent, and adds a catalyst and a dehydrating agent for dehydration cyclization to form the triphenylamine-containing structure of the present invention. The double horses are made of imine compounds. Examples of the catalyst include 'synthesis (acetic acid phantom test catalyst; examples of the dehydrating agent include, (4) _ vinegar cover kitchen. The dehydration cyclization reaction of this step (Β) is usually carried out under the conditions of 70 to 1201 (five) = Compared with (4) at f hours, preferably about 10 to 12 hours, the novel compound of the bismaleimide containing the tris-amine structure of the present invention can be obtained by dripping into ice water.醯i imidization 110300 1335917 = triphenyl fluorene bismaleimide polymer. Example of the material Γ·;, double isobutyronitrile coffee, or diphenyl peroxide brewing = ^ ^ ^ 70 To the boot, preferably in the ❹ (10) ......, the cow is simmered, the reaction can be terminated by adding methanol, and finally, the double-maline-branched &w" (4) The embodiment 'further describes the features and effects of the present invention' but is not intended to limit the present invention. EXAMPLES Example 1 After flushing 250 ml of a three-necked round bottom flask equipped with a feeding tube with nitrogen gas, 2.057 g (20.98 mmol) of the acid liver was added to the solution (20 liters). Adding the three-necked round bottom flask; then, via the feeding tube, 3. gram (9.99^mol) 4,4,-diamino-4, '-cyanotriphenylamine
獲 3C 紅 酮溶液（70毫升）緩慢滴加人此三頸圓底燒瓶内。於常溫 與通氮氣常壓的條件下攪拌進行反應，歷時12小時。反 應完成後，藉由過濾方式將固體，並以丙^清洗濾餅 得4.545克之紅色固體產物，產率92%。經11]丽1^、 NMR、與C-H HMQC鑑定（參考第ία、1Β圖與第2圖） 色固體產物為Ν，Ν-雙（4-醯胺酸）-4-氰基苯胺。 使用氮軋沖滌2 5 0毫升配有加料管之三頸圓底燒瓶 並將其置於油浴槽。將4. 959克（9. 99毫莫耳）N，N-雙（4_ 醯胺酸）-4-氰基苯胺之丙酮溶液（4〇毫升）、〇 492克 (5.99毫莫耳）無水乙酸鈉加入該三頸圓底燒瓶。接著， 經由加料管滴加8· 157克（79. 90毫莫耳）乙酸酐。緩慢升 110300 10 1335917 .溫至8{rc與通氮氣之常壓下，迴流攪拌10小時，最後加 入冰水擾拌可終止反應。使用500毫升之去離子水洗滌三 次後’使用85毫升之丙酮進行再結晶，獲得3 5〇〇克之 黃色固體產物，產率76%。經1H NMR、13C NMR、C_H HMQC、 .與1R鑑定（參考第3A、3B圖與第4 ' 5圖），黃色固體產 物為N，N-雙（4-馬來醯亞胺苯基）-4-氰基苯胺，以熱分析 儀（DSC: differential scanning calorimetry)進行鑑定 與分析’其熔點為242〜244°C (參考第6圖）。 _實施例2 以氮氣沖沖滌100毫升之三頸圓底燒瓶，並置於槽 内。將0. 500克（1. 〇9毫莫耳）實施例1所製得之N，N-雙 (4-馬來醯亞胺苯基）-4-氰基苯胺之NMP溶液（5毫升）、 〇· 713克（4. 344毫莫耳）起始劑AIBN直接加入該三頸圓底 燒瓶内’再緩慢升溫至90°C，並於9(TC條件下迴流授拌 3小時。倒入曱醇終止反應，再以2 0 0毫升之甲醇熱萃純 鲁、化三次’最後獲得〇. 489克之褐色固體產物，聚[N, N-雙 (4-馬來醯亞胺笨基）-4-氰基苯胺]，產率為98% 。 j則試例1 根據表1所列，分別取2毫克實施例1與實例2所製 得之N，N-雙（4-馬來醯亞胺苯基）-4-氰基苯胺以及聚 [N，N-雙（4-馬來醯亞胺苯基）-4-象基苯胺]溶於2毫升溶 劑中，進行溶解性測試，測試結果記錄於表1。 11 110300 1335917 第2圖係本發明實，施例1之中間產物N, N-雙（4-醯胺 酸）_4 -氮基苯胺之C-H HMQC圖譜； 第3Α與3Β圖係本發明含三苯胺結構之雙馬來醯亞胺 化合物之1Η丽R圖譜與13C NMR圖譜； 第4圖係本發明含三苯胺結構之雙馬來醯亞胺化合 物之C-H HMQC圖譜； 第5圖係本發明含三苯胺結構之雙馬來醯亞胺化合 物之IR圖譜；以及 第6圖係本發明含三苯胺結構之雙馬來醯亞胺化合 物之熱分析（DSC)結果。A 3C red ketone solution (70 ml) was slowly added dropwise to the three-necked round bottom flask. The reaction was carried out under stirring at normal temperature under a nitrogen atmosphere at normal pressure for 12 hours. After completion of the reaction, the solid was filtered and the cake was washed with <RTI ID=0.0>> It was identified by 11], NMR, and C-H HMQC (refer to ία, 1 与 and 2). The color solid product was hydrazine, bis-bis(4-proline)-4-cyanoaniline. A 250 ml three-necked round bottom flask equipped with a feed tube was purged with nitrogen and placed in an oil bath. 4. 959 g (9. 99 mmol) of N,N-bis(4-proline)-4-cyanoaniline in acetone (4 mL), 492 g (5.99 mmol) of anhydrous acetic acid Sodium was added to the three-necked round bottom flask. Next, 8·157 g (79.90 mmol) of acetic anhydride was added dropwise via a feeding tube. Slowly rise 110300 10 1335917. Warm to 8{rc and under nitrogen at atmospheric pressure, reflux for 10 hours, and finally add ice water to disturb the reaction to terminate the reaction. After washing three times with 500 ml of deionized water, 'recrystallization was carried out using 85 ml of acetone to obtain 35 g of a yellow solid product in a yield of 76%. Identification by 1H NMR, 13C NMR, C_H HMQC, and 1R (refer to Figures 3A, 3B and 4 '5), the yellow solid product is N,N-bis(4-maleiminephenyl)- 4-cyanoaniline was identified and analyzed by a thermal analyzer (DSC: differential scanning calorimetry), and its melting point was 242 to 244 ° C (refer to Fig. 6). - Example 2 A 100 ml 3-neck round bottom flask was purged with nitrogen and placed in a tank. 0. 500 g (1. 〇9 mmol) of N,N-bis(4-maleimidophenyl)-4-cyanoaniline NMP solution (5 ml) obtained in Example 1. 〇· 713 g (4. 344 mmol) of the initiator AIBN was directly added to the three-necked round bottom flask, and then slowly warmed to 90 ° C, and refluxed for 3 hours under TC conditions. The reaction was terminated by decyl alcohol, and then purified by hot extraction with 200 ml of methanol for three times to obtain the final product of 489 g of brown solid, poly[N, N-bis(4-maleimide). 4-cyanoaniline], yield 98% j. Test Example 1 According to Table 1, 2 mg of N,N-bis (4-malian) prepared in Example 1 and Example 2, respectively. Amine phenyl)-4-cyanoaniline and poly[N,N-bis(4-maleimidophenyl)-4-indenylaniline] are dissolved in 2 ml of solvent for solubility test, test results Recorded in Table 1. 11 110300 1335917 Figure 2 is a CH HMQC pattern of the intermediate product N, N-bis(4-proline) _4-nitroaniline of Example 1, the third and third Β diagrams 1 RR R spectrum and 13C N of the bismaleimine compound containing triphenylamine structure of the invention MR map; Fig. 4 is a CH HMQC pattern of the bismaleimide compound containing a triphenylamine structure of the present invention; Fig. 5 is an IR spectrum of the bismaleimide compound containing a triphenylamine structure of the present invention; Figure 6 is a thermal analysis (DSC) result of the bimaleimide compound containing a triphenylamine structure of the present invention.
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