CN100400525C - N-缩水甘油基胺的制备方法 - Google Patents
N-缩水甘油基胺的制备方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
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- C07D303/02—Compounds containing oxirane rings
- C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
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- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Epoxy Resins (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明描述了一种制备芳族N-缩水甘油基胺的方法，其中使用溶解于碳酸丙二醇酯中的硝酸的二价或多价金属盐作为催化剂，将胺与表氯醇一起加热，随后将产物脱卤化氢，所述胺包含至少一个芳氨基氢原子，所述表氯醇的用量为每当量所述芳胺的氨基氢至少0.7当量。
Description
本发明涉及一种制备芳族N-缩水甘油基化合物的方法以及通过该方法得到的N-缩水甘油基胺，所述N-缩水甘油基化合物特别是那些每分子形式平均具有一个以上缩水甘油基的环氧树脂。
环氧树脂通常用作粘合剂、涂料、铸塑用料和绝缘材料以及增强的复合材料，并且大量不同化学结构的环氧树脂可购自商品。这些树脂通常为缩水甘油基醚或缩水甘油基酯，由表氯醇与双酚或二羧酸制备。对于需要良好高温性能的用途(例如用于航空工业)而言，通常优选具有与芳族氨基的氮原子相连的缩水甘油基的树脂。这类物质通过以下方法制备：将芳胺与每当量氨基氢原子约0.8-10当量的表氯醇反应，随后用碱对得到的产物进行常规的脱氯化氢。该反应可在没有催化剂的情况下进行，或者如US 4,540,769中所述在酸性催化剂存在下进行。
尽管通常具有令人满意的性能，但是通过已知方法制备的N-缩水甘油基胺及其制备方法本身还可进一步改进。例如对于常规方法制备的N-缩水甘油基胺，一种不足之处在于可能由于制备过程中的副反应导致N-缩水甘油基胺通常非常粘，即发生了偶联反应而不是所需的缩水甘油化反应。难以使用这种粘性树脂，特别是在制备纤维增强复合材料或铸塑用料时，以致通常需要使用惰性稀释剂来降低粘度。通常不希望使用稀释剂。活性稀释剂为那些与固化剂反应并且保留在已交联树脂中的稀释剂。其对固化树脂的性能有不利的影响。在固化前通过蒸发除去惰性稀释剂，通常会造成燃烧或毒性危害。此外，除非从树脂中完全除去惰性稀释剂，否则其可影响固化树脂的性能。在本文使用的方法中，特别是在工业规模的方法中，也对使用溶剂相当感兴趣，特别是用作催化剂的溶剂，该溶剂无需特殊的安全措施或无需其他处理。最后，特别优选使用镧催化剂得到所需的高催化活性。
现已发现使用溶解于碳酸丙二醇酯的硝酸的二价或多价金属盐作为催化剂进行芳胺的N-缩水甘油化的方法具有令人惊奇的优点。本发明方法的一种令人惊奇的优点在于与使用2-甲氧基乙醇作为该催化剂的溶剂相比，反应发生更快。本发明方法的另一种令人惊奇的优点在于与使用文献中已知的催化剂的溶剂相比，所述反应的副产物更少。
因此，本发明涉及一种制备芳族N-缩水甘油基胺的方法，其中使用溶解于碳酸丙二醇酯中的硝酸的二价或多价金属盐作为催化剂，将胺与表氯醇一起加热，随后将所述产物脱卤化氢，所述胺包含至少一个芳氨基氢原子、优选至少两个芳族氨基氢原子，所述表氯醇的用量为每当量所述芳胺的氨基氢至少0.7当量、优选至少0.8-1.5当量。优选先将所述催化剂完全溶解于碳酸丙二醇酯，随后再加至反应混合物中。例如可使用5-40％重量的硝酸镧的碳酸丙二醇酯溶液。
用作本发明方法的催化剂的硝酸盐优选为元素周期表IIa、IIb、IIIb、VIIb或VIII族金属的盐，所述盐也可为水合物形式。特别优选镁、钙、锌、锰、镍、镧、钒(以氧钒根形式)、镱和铀(以双氧铀根形式)的硝酸盐。尤其特别优选硝酸镧，特别是其六水合物形式。
所述反应混合物的催化剂的用量通常为所述芳胺重量的0.1％-10％，特别是0.4-2％。
本发明的缩水甘油化的芳胺可仅包含伯氨基、仅包含仲氨基或包含伯氨基和仲氨基，这些氨基与芳环直接连接，所述芳胺可包含一个或多个芳环。这些芳环也可被其他基团取代，例如烷基(特别是具有1-4个碳原子的烷基)、具有1-4个碳原子的亚烷基、磺酰基、卤原子、羟基、具有1-4个碳原子的烷氧基和叔氨基。在本发明方法中，优选使用具有一个或两个伯氨基的胺。具体而言，特别优选的是苯胺、氨基苯基茚满和式(I)或(II)的胺，
其中
R1、R2、R3和R4相同或不同，为具有1-4个碳原子的烷基或氢原子，X为键、具有1-4个碳原子的亚烷基、氧原子、硫原子或羰基或磺酰基。优选胺的实例有苯胺、1，3，3-三甲基-1-(4-氨基苯基)-5-氨基茚满、1，3，3-三甲基-1-(4-氨基苯基)-6-氨基茚满、邻苯二胺、间苯二胺、对苯二胺、2，4-二乙基-6-甲基-1，3-苯二胺、二(4-氨基苯基)甲烷、二(4-氨基苯基)酮、二(4-氨基苯基)醚、二(4-氨基苯基)硫醚、联(3-氨基苯)和二(4-氨基苯基)砜、4，4’-二氨基-3-乙基二苯基甲烷和二(4-氨基-3-乙基苯基)甲烷，尤其特别优选苯胺和二(4-氨基苯基)甲烷。
所述反应通常在升高的温度(具体为50-100℃)下在惰性有机溶剂中进行，所述有机溶剂例如为甲苯或二甲苯。表氯醇和催化剂可一次性加入或分批加入。胺与表氯醇之间的反应完成后(通常在约1-5小时后)，通常采用常规的方法加入氢氧化钠或氢氧化钾以及任选的卤化季铵盐(例如氯化苄基三甲铵)作为催化剂脱氯化氢。在50-100℃下加热2-10小时后，用水洗涤该反应混合物，除去水相，由有机相得到所需的N-缩水甘油基胺。粗产物可直接使用或通过常规方法纯化后使用。
通过本发明方法得到的含N-缩水甘油基的环氧树脂可使用常规的方法固化。适用于包含N-缩水甘油基的环氧树脂的固化剂为众所周知的固化剂，例如有双氰胺、芳胺(例如联(3-氨基苯)和二(4-氨基苯基)砜和二(4-氨基苯基)甲烷(通常与固化促进剂一起使用，所述固化促进剂例如为胺的BF3络合物))和聚羧酸酐(如环己烷-1，2-二羧酸酐、甲基二环[2.2.1]庚-5-烯-2，3-二羧酸酐、均苯四酸二酐和二苯甲酮四羧酸二酐。
以下实施例进一步解释本发明。除非另有说明，否则所有的份数和百分数以重量计。粘度的测定按照ASTM-0445进行(Cannon-Fenske粘度计，#650，50℃)。
实施例1
在搅拌下将二(4-氨基苯基)甲烷(100g)的200ml甲苯溶液和2.5g20％的六水合硝酸镧的碳酸丙二醇酯溶液加热至55℃。在210分钟内计量加入表氯醇(208g)，随后在搅拌下将该反应混合物在80℃下再加热15小时。
将该混合物冷却至70℃，加入1.5g氯化苄基三甲铵。在180分钟内计量加入50％的氢氧化钠溶液(177g)，随后加入水(326g)。分离除去水相，用130g甲苯稀释有机相并用1％的磷酸二氢钠(75g)和水(175g)洗涤。在110℃下真空(30mbar)蒸发甲苯溶液，残留物与0.5gHyflo Super
(kieselgur，得自Fluka)混合并过滤。该N-缩水甘油基胺的环氧化物含量为8.87当量/kg(理论值的82％)，在50℃下粘度为4270mPas。
实施例2
重复实施例1，不同之处在于六水合硝酸镧以研碎的粉末形式加入该胺的甲苯溶液中。该N-缩水甘油基胺的环氧化物含量为8.77当量/kg(理论值的80％)，在50℃下粘度为4600mPas。
实施例3
在一系列试验中，测定了两个受反应的动力学和选择性影响的参数。反应条件与实施例1相同，催化剂在甲苯、2-甲氧基乙醇、碳酸乙二醇酯、γ-丁内酯或按照本发明在碳酸丙二醇酯中加入。
表1各种硝酸镧溶液的催化活性比较
| 溶剂 | 计量加料结束后的累积 | 结晶时间(小时) |
| 甲苯 | 0.33 | 6:46 |
| 2-甲氧基乙醇 | 0.22 | 7:18 |
| 碳酸乙二醇酯 | 0.24 | 4:45 |
| γ-丁内酯 | 0.23 | 6:00 |
| 碳酸丙二醇酯 | 0.20 | 3:45 |
在计量加料结束后表氯醇的累积体现出转化率的高低。累积少的话，则反应速度快，即具有高催化活性。
通过每摩尔二(4-氨基苯基)甲烷加入4摩尔表氯醇形成取代的表氯醇。结晶时间提供了有关转化率和选择性(纯度)的信息，时间越短越好。
Claims (7)
1.一种制备芳族N-缩水甘油基胺的方法，其中使用溶解于碳酸丙二醇酯中的硝酸的多价金属盐作为催化剂，将胺与表氯醇一起加热，随后将产物脱氯化氢，所述胺包含至少一个芳氨基氢原子，所述表氯醇的用量为每当量所述芳胺的氨基氢至少0.7当量。
2.权利要求1的方法，其中使用的催化剂为硝酸镧或水合硝酸镧。
3.权利要求1的方法，其中将所述催化剂完全溶解于碳酸丙二醇酯中，随后再加入所述反应混合物中。
4.权利要求1的方法，其中所述胺为苯胺或二(4-氨基苯基)甲烷。
5.权利要求1的方法，其中所述表氯醇的用量为每当量所述芳胺的氨基氢0.8-1.5当量的表氯醇。
6.权利要求1的方法，其中每100重量份芳胺使用0.1至10重量份所述催化剂。
7.权利要求1的方法，其中使用的催化剂为硝酸的二价金属盐。
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| TWI331998B (en) | 2010-10-21 |
| DE602004009458D1 (de) | 2007-11-22 |
| EP1656363B1 (en) | 2007-10-10 |
| EP1656363A2 (en) | 2006-05-17 |
| US8076495B2 (en) | 2011-12-13 |
| ES2293328T3 (es) | 2008-03-16 |
| TW200505885A (en) | 2005-02-16 |
| KR101126137B1 (ko) | 2012-03-29 |
| DE602004009458T2 (de) | 2008-07-24 |
| WO2005003109A2 (en) | 2005-01-13 |
| RU2378265C2 (ru) | 2010-01-10 |
| WO2005003109A3 (en) | 2005-03-31 |
| RU2006102556A (ru) | 2006-08-27 |
| JP4658930B2 (ja) | 2011-03-23 |
| KR20060035646A (ko) | 2006-04-26 |
| ATE375335T1 (de) | 2007-10-15 |
| US20080221342A1 (en) | 2008-09-11 |
| JP2009513536A (ja) | 2009-04-02 |
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