200909427 九、發明說明： 【發明所屬之技術領域】 ‘心Γ月：有關一種雙馬來酿亞胺化合物及其製法，尤 其t關—種具有不對稱結構之雙馬來亞酸胺化合物及 【先前技術】 聚醯亞胺化合物熱穩定性高且 械強度、及抗化學腐钱性，常用於緣性、機 子7肉蚀往吊用於多種電子加工材料。 椹…而但由於傳統醯亞胺分子中的對稱與高度社曰社 ::::二的醯亞胺化合物不易溶於低沸 — 例如"基+ m妝寺寺由於該也高沸點非所工 極性溶液劑不易移除，往往會殘存於加工^^^貝二 幅降低產品的機械性質與耐熱性質。 “中’大 機方面、由㈣亞胺化合物本身不易溶於低海點有 故不易與其他化合物或聚合物搭配推合使用， 制了 S&亞胺化合物的應用。 =具有優異溶解性之改質㈣胺化合物，乃 生’付合工業實務應用的殷切需求。 【發明内容】 於上述問題，本發明之主暴日+ 供田一妨L &个知3之主要目的在於提供一種具有 k兴洛解性之雙馬來醯亞胺化合物。 本發明之另一目的’係提供一種具有優異耐熱性與難 …性之雙馬來醯亞胺化合物。 、 110300 6 200909427 本發明之另一目的，係提供— 學特性之雙馬來醯亞胺化合物。 種可用於有效改善 電化 種如式（ 為 所示含 了達上述及其他目的，本發明揭露 二笨胺結構之雙馬來醯亞胺化合物200909427 IX. Description of the invention: [Technical field to which the invention belongs] 'Heart month: a kind of bimale-branched imine compound and its preparation method, especially t-a kind of bimaleic acid amine compound with asymmetric structure and Prior Art] Polyimine compounds have high thermal stability and mechanical strength, and are resistant to chemical rot, which are often used for edge and machine 7 erosive hoisting for a variety of electronic processing materials.椹...but because of the symmetry in the traditional bismuth imine molecule and the high 曰 : :::: bis quinone imine compound is not easily soluble in low boiling - for example, " base + m makeup temple because of this high boiling point The working polar solution is not easy to remove, and often remains in the processing of ^^^Bei to reduce the mechanical properties and heat resistance of the product. "In the middle of the machine, the (4) imine compound itself is not easily soluble in the low sea point, so it is not easy to use with other compounds or polymers, and the application of S& imine compounds is made. The main purpose of the present invention is to provide a kind A double-maleimide compound of the present invention. Another object of the present invention is to provide a bismaleimide compound having excellent heat resistance and difficulty. 110300 6 200909427 Another object of the present invention is Providing a bimaleimide compound having the characteristics of the present invention. The species can be used to effectively improve the electrochemical species such as the formula (for the above-mentioned and other purposes, the present invention discloses a bimaleimide compound having a di-ammine structure.
、、^ί中，/為氰基。該化合物係利用二胺與馬來酸酐於 進打反應形成醯胺酸，再於催化劑存在之條件下， 進行環化脫水反應㈣成之絲。絲三苯胺結構之’ 來酿亞胺化合物具有優異的溶解性，可溶於傳統低彿ς之 :機溶劑’可改善或簡化雙馬來醒亞胺之後續成膜與加工 製程。另一方面、該化合物亦具有良好的難燃性與耐熱 I1 生可用作為難燃劑或用於改質樹脂之耐燃特性。再者、 2化合物之拉電子特性，可應用於電子產品之加工，提高 電子材料之介電常數，並調整電化學特性。 【實施方式】 本發明揭示一種含三苯胺結構之新穎雙馬來醯亞胺 化合物及其製法，該化合物具有式（I )所示之結構： 110300 7 200909427, , ^ί, / is cyano. The compound is formed by reacting a diamine with maleic anhydride to form a valine acid, and then performing a cyclization dehydration reaction (4) into a filament in the presence of a catalyst. The silk triphenylamine structure has excellent solubility and is soluble in the traditional low-fossil: the organic solvent can improve or simplify the subsequent film formation and processing of the bumamine. On the other hand, the compound also has good flame retardancy and heat resistance. It can be used as a flame retardant or as a flame retardant property of a modified resin. Furthermore, the electronic properties of the 2 compounds can be applied to the processing of electronic products, increase the dielectric constant of electronic materials, and adjust the electrochemical characteristics. [Embodiment] The present invention discloses a novel bismaleimide compound containing a triphenylamine structure and a process for producing the same, which has the structure represented by the formula (I): 110300 7 200909427
其中，R為氰基。 本發明亦揭示一種製造含三苯胺結構之新穎雙馬來 醯亞胺化合物之方法，包括下列步驟： (A)由式（π )所示，4, 4’-二胺基-4’，-氰基三苯基胺之 二胺化合物與馬來酸酐以1 : 2之莫耳比於溶劑中，進行 反應形成醯胺酸化合物；以及Wherein R is a cyano group. The invention also discloses a method for producing a novel bismaleimide compound containing a triphenylamine structure, comprising the following steps: (A) 4,4'-diamino-4', as represented by the formula (π), a diamine compound of cyanotriphenylamine and maleic anhydride are reacted in a molar ratio of 1:2 to form a proline acid compound;
(Π ) 一 添加催化劑使該醯胺酸進行脫水環化反應，形成 含三笨胺結構之新穎雙馬來醯亞胺化合物。 化學反應式如下所示：(Π) A novel catalyst is used to subject the proline to a dehydration cyclization reaction to form a novel bismaleimide compound having a tris-amine structure. The chemical reaction formula is as follows:
本發明之方法中， 但非限於酮類溶劑In the method of the present invention, but not limited to ketone solvents
步驟（A)所使用 例如丙酮、 之溶劑的實例包 曱基乙基酮、曱基異 110300 8 200909427 丁基酮及乙酸乙酯；以及非質子高温極性溶劑，例如二曱 基甲醯胺或二甲基乙醯胺。 通吊，步驟（A)係於〇至4〇°c之溫度範圍内進行反 應，較佳係於15至啊之溫度範圍内進行反應；溫度過 局會使中間產物醯胺酸產生閉環的現象，而無法在後續反 應中順利形成本發明之新穎雙馬來酸亞胺化合物；一般而 言、在常溫常Μ之條件下進行該步驟（A)之反應即可。 ，步驟⑴之反應日㈣並無特別限制，只要能形成中 間產物醯胺酸即可。一妒‘止、 般而5，步驟（A)之反應時間係介 於6至2 4小時，較佳传介私β 利用過遽的方式分離出中2小時°反應完成後， 即可進行句m 胺酸，經純化洗膝後， r J進仃步驟（B)之脫水環化反應。 驟’該步驟⑻之脱水環化反應係將步 遲订脫水％化，形成本發明 化合物。催化劑的m “構之雙馬來醯亞胺 化，m3匕括’乙酸鋼（贈酸納）等驗性催 化I錢水叙實例包括，但非限於醋酸酐。 该步驟⑻之脫水環化反應通 度條件下進行，較佳係於8〇 /至12仏之- 約8 f 丨。士 主100c之溫度條件下進行 丄=广較佳約1(1至12小時，再以滴入冰水的 万式終止反應，即可獲得本發明含二 ^ 亞胺新穎化合物。 —本胺m構之雙馬來醯 本發明含三笨胺結構之雙 溶劑存在^ ”、、束鲶亞私化合物亦可於 木件下，添加起始劑，加熱進行聚合反應，形 110300 200909427 成含三苯胺結槿雔 包括，但非限於偶：二'鷇亞胺聚合物。該起始劑的實例 (湖。該聚合反;猜（讀）、或過氧化二苯甲醒 亡之加熱料至跳’較佳係於別至⑽ 得含三苯料構 人^卩可終錢應，最後、獲 、耳妆〜構之雙馬來醯亞胺聚合物。 =下係藉由特定之具體實施例 特點與功效，作非用mi /况明本發明之 —非用於限制本發明之範疇。 實施例 f 貫施例1 使用氮氣沖滌250毫升配有加料管 瓶，之後、將？ ης7 A τ B怎一工貝0底燒 、2.057克（2〇.98毫莫耳）馬來酸肝 液〔2fi謇斗u 1 /刁+馱酐之丙酮溶 毛升）加入該三頸圓底燒瓶 3.000 ^(9 , 、'工由加枓官將 兄笔旲耳）4,4，_二胺基_4”_ 酮溶液（70亳升、绥r龙丄 土 一本月女之丙 ^ a ^ 升）緩反滴加入此三頸圓底燒瓶内。於常、、田 與通氮氣常壓的條件下橹挫 韦’皿 進订反應，歷時12小時。及 獲 應元成後’藉由過滅方式脾田辦 、， 巧 巧万式將固脰，亚以丙酮清洗濾餅 侍4.545克之紅色固體產物，產率似。經A· NMR、與c-H HMQC梦定ί夫去裳id 队‘疋（麥考弟ΙΑ、1B圖與第2圖），紅 色固體產物為N，N-雙（4-醯胺酸）-4-氰基苯胺。 、，使用氮氣沖滌250毫升配有加料管之三頸圓底燒瓶 =將其置於油浴槽°將U59克（9· 99毫莫耳）N，N-雙（4_ 醯胺酸兴4—氰基苯胺之丙酮溶液（40毫升）、0.492克 (5.99笔莫耳）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. 9〇毫莫耳）乙酸酐。緩慢升 110300 10 200909427 溫至80 °C與通氮氣之常壓下，迴流攪拌l〇小時，最後加 入冰水攪拌可終止反應。使用5 0 0毫升之去離子水洗蘇二 次後，使用8 5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IR鑑疋（參考弟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1 0 0毫升之三頸圓底燒瓶，並置於槽 内。將0. 500克（1. 09毫莫耳）實施例1所製得之N, N一雙 (4-馬來酸亞胺苯基）_4-氰基苯胺之丽p溶液（5毫升）、 0. 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9(rc，並於⑽乞條件下迴流攪拌 3小時。倒入曱醇終止反應，再以200毫升之曱醇熱萃純 (化三次，最後獲得〇. 489克之褐色固體產物，聚[N，N—雙 (4-馬來酸亞胺苯基）_4__氰基苯胺]，產率為⑽％ 。 .測試例Ί 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-馬來驢亞胺苯基）_4_氰基苯胺以及聚 [N，N-雙（4-馬來醯亞胺苯基）_4_氰基苯胺]溶於2亳升溶 劑中，進行溶解性測試，測試結果記錄於表1。 110300 11 200909427 表1 溶劑 DMAc DMF DMSO Cresol THF~~MeOH CHCl·Examples of the solvent used in the step (A) include acetone, a solvent such as ethyl ketone, decyl iso-110300 8 200909427 butyl ketone and ethyl acetate; and an aprotic high-temperature polar solvent such as dimercaptomethylamine or two Methylacetamide. Passing, step (A) is carried out in the temperature range of 〇 to 4 ° °c, preferably in the temperature range of 15 to ah; temperature reaction will cause the intermediate product glutamic acid to produce a closed loop phenomenon However, the novel bis-maleic acid imide compound of the present invention cannot be smoothly formed in the subsequent reaction; generally, the reaction of the step (A) can be carried out under normal temperature and normal conditions. The reaction day (4) of the step (1) is not particularly limited as long as the intermediate product proline is formed. The reaction time of step (A) is between 6 and 24 hours. It is better to pass the private β to separate the mixture for 2 hours. After the reaction is completed, the sentence can be carried out. m Amino acid, after purification and washing the knee, r J is subjected to the dehydration cyclization reaction of the step (B). The dehydration cyclization reaction of this step (8) is stepwise dehydrated to form a compound of the present invention. Examples of catalysts such as bismaleimide, m3, including 'acetate steel (sodium acid), etc., include, but are not limited to, acetic anhydride. Dehydration and cyclization of this step (8) It is preferably carried out under the conditions of fluency, preferably between 8 〇 / 12 仏 约 约 丨 丨 丨 丨 丨 丨 士 士 士 士 士 士 士 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 The novel compound containing the bis-imine of the present invention can be obtained by terminating the reaction. The double amine of the present invention is a double solvent of the present invention, and the presence of a double solvent containing a tris-amine structure. Under the wood, the initiator can be added and heated to carry out the polymerization reaction. The shape of 110300 200909427 into a triphenylamine-containing crucible includes, but is not limited to, an even: bis-imine polymer. An example of the initiator (lake. The polymerization is reversed; the guessing (reading), or the heating of the diphenyl peroxide dying to the jump 'better' is better than the (10) to contain the triphenyl material structure ^ ^ can be the final money should be, finally, get, ear makeup ~ 构 双 马 醯 醯 醯 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The invention is not intended to limit the scope of the invention. Example f Example 1 Using a nitrogen purged 250 ml bottle with a feeding tube, after which, η ς 7 A τ B is burned, 2.057 g (2 〇.98 millimoles) Maleic acid liver liquid [2fi u u u 1 / 刁 + 驮 之 之 之 溶 ) ) ) ) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 4,4,-diamino- 4"-ketone solution (70 liters, 绥r long 丄 一 一 一 ^ ^ ^ a a a a a a a a a ^ ^ ^ ^ ^ 加入 加入 加入 加入 加入 加入 加入 加入 加入 加入 加入 加入 加入 加入 加入Under the conditions of normal pressure, nitrogen gas and normal pressure under the conditions of nitrogen, atmospheric pressure, it took 12 hours to complete the reaction, and after receiving the Yuanyuancheng, the spleen was done by the method of annihilation.脰, the acetone filter cake washed 4.545 grams of red solid product, the yield is similar. After A · NMR, and cH HMQC dreaming ί 去 裳 id id team '疋 (Mcco, 1 1B and 2) The red solid product was N,N-bis(4-proline)-4-cyanoaniline., using a nitrogen purged 250 ml three-necked round bottom flask equipped with a feeding tube = placed in an oil bath ° U59 grams (9·9 9 mmoles of N,N-bis(4_proline acid 4-cyanoaniline in acetone (40 ml), 0.492 g (5.99 mol) anhydrous sodium acetate was added to the three-necked round bottom flask. 8. 157 g (79. 9 〇 mmol) of acetic anhydride was added dropwise via a feeding tube. Slowly rise 110300 10 200909427 Warm to 80 ° C under normal pressure with nitrogen, reflux for 1 hour, and finally add ice water to stir. The reaction can be terminated. After washing twice with 500 ml of deionized water, recrystallization is carried out using 8 5 ml of acetone to obtain a 3,5 g of a yellow solid product yield 76%. By 1H NMR, 13C NMR, CH HMQC, 'with IR 疋 (Refer to 3A, 3B and 4, 5), the yellow solid product is N, N-bis (4-maleimine phenyl) -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 10-neck round-bottomed flask of 100 ml was purged with nitrogen and placed in a tank. 0. 500 g (1. 09 mmol) of the N,N-bis(4-maleimidophenyl)-4-cyanoaniline solution (5 ml) obtained in Example 1, 0. 713 g (4. 344 mmol) of the initiator AIBN was directly added to the three-necked round bottom flask, and the temperature was slowly raised to 9 (rc, and refluxed under reflux conditions of (10) for 3 hours. The reaction was further purified by hot extraction with 200 ml of decyl alcohol (three times, finally 〇. 489 g of a brown solid product, poly[N,N-bis(4-maleimidophenyl)_4_-cyanoaniline]] The yield was (10)%. Test Example Ί According to Table 1, 2 mg of N,N-bis(4-maleimidophenyl)_4-cyanide prepared in Example 1 and Example 2, respectively. The aniline and poly[N,N-bis(4-maleimidophenyl)_4-cyanoaniline] were dissolved in 2 liters of solvent for solubility test, and the test results are reported in Table 1. 110300 11 200909427 Table 1 Solvent DMAc DMF DMSO Cresol THF~~MeOH CHCl·
土表不加熱時可部份溶解或膨潤（swel丨ing) —表示加熱時亦不能溶解 根據表1結果顯示，本發明含三苯胺結構之雙馬來醯 亞胺具有不對稱性之分子結構’大幅改善了該馬來醯亞胺 =物對極性溶劑的溶解度，可溶於各種常見之低滞點有 機冷刈，另一方面、該雙馬來醯亞胺經聚合所形成之肀人 物，同樣具有不對稱性結構，相較於傳統聚 ：口 ^:具㈣佳之溶解性，如上表所示，該聚合物^溶 於大部分常見之極性溶劑中。 由於本發明含三笨胺結構之雙馬來 再T種常見之低涛點有機溶劑，且具有良好:::性易 :者、由於本發明之雙馬來醒亞胺化合 ， 性，可用作為難燃劑或用於改善其他聚合熱穩 難燃與耐熱特性。 ’衣氧树脂之 【圖式簡單說明】 施例1之中間產物Ν，Ν—雙 NMR圖譜與】3C NMR圖譜； 第1A與1 β圖係本發明實 (4 一醯胺酸）-4-氰基苯胺之ιΗ 11〇3〇〇 12 200909427 第2圖係本發明I a 酸）-4-氰基苯胺之Γ例1之中間產物N，N-雙（4-醯胺 第 HHMQC 圖譜； 弟與3B圖係太' 化合物之1Η _圖心'明含三苯胺結構之雙馬來醒亞胺 味Α 口 δθ與X NMR圖譜； 弟4圖係本發明人_ 物之C-H _圖譜/二苯胺結構之雙馬來釀亞胺化合 ^圖T才么明含二苯胺結構之雙馬來醯亞胺化合 物之IR圖譜；以及 第6圖係本發明含二苯胺結才籌之雙馬來酸亞胺化合 物之熱分析（DSC)結果。 110300 13When the soil surface is not heated, it can be partially dissolved or swelled. It means that it cannot be dissolved even when heated. According to the results of Table 1, the molecular structure of the amphetamine of the present invention containing a triphenylamine structure has asymmetry. Significantly improved the solubility of the maleimide = substance in a polar solvent, soluble in various common low-stagnation organic cold headings, and on the other hand, the formation of the double-maleimide by polymerization, the same It has an asymmetrical structure, which is soluble in most common polar solvents, as shown in the above table, compared to the conventional poly(:). Since the present invention contains a double-mole-amine structure, it is a common low-point organic solvent, and has good:::sexuality: due to the double-mammalization of the present invention, the sex can be used as A flame retardant or used to improve the heat and flame retardancy and heat resistance of other polymerizations. 'Esophageal resin' (simplified illustration) The intermediate product of Example 1 is Ν, Ν-double NMR spectrum and 3C NMR spectrum; 1A and 1 β diagram is the present invention (4-proline)-4-氰 氰 Η 〇 〇 〇 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 With the 3B diagram is too 'compound 1 Η _ heart ' ming with triphenylamine structure of the double horse to wake up imine miso mouth δθ and X NMR spectrum; brother 4 diagram is the inventor _ CH of the spectrum _ map / diphenylamine The structure of the double-male-immobilized imine compound ^ Figure T is the IR spectrum of the dimaleimide compound containing the diphenylamine structure; and the sixth figure is the di-maleic acid containing the diphenylamine complex of the present invention. Thermal analysis (DSC) results for amine compounds. 110300 13