CN100471855C - 含有顺丁烯二酰亚胺官能团的氧杂环丁烷化合物 - Google Patents
含有顺丁烯二酰亚胺官能团的氧杂环丁烷化合物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Pyrrole Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Plural Heterocyclic Compounds (AREA)
- Epoxy Compounds (AREA)
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Abstract
本发明涉及含有氧杂环丁烷官能团和顺丁烯二酰亚胺官能团的化合物。所述氧杂环丁烷官能团在阳离子或阴离子开环反应中是可均聚的，所述顺丁烯二酰亚胺官能团是可均聚的，或与化合物如供电子体化合物发生聚合。双官能团便于双重固化加工。化合物结构如下：其中，R1是甲基或乙基，R2是二价烃基，X和Y各自独立地为直接键，或醚，酯，酰胺或氨基甲酸酯基团，和Q是二价有机基团，条件是X和Y不同时为直接键。
Description
发明领域
本发明涉及含有顺丁烯二酰亚胺官能团的氧杂环丁烷化合物。
发明背景
氧杂环丁烷类是高反应活性的环醚，其既能够进行阳离子也能够进行阴离子开环均聚反应。顺丁烯二酰亚胺化合物可以发生自由基聚合反应。
发明概述
本发明涉及含有氧杂环丁烷官能团和顺丁烯二酰亚胺官能团的化合物。这些化合物可以在反应中发生均聚，其中所述氧杂环丁烷能够进行阳离子或阴离子开环，或与化合物如供电子体化合物发生聚合。双官能团便于双重固化加工，既可以进行热固化也可以进行辐射固化。这种性能使得其在许多方面，如胶粘剂，涂料，密封剂和复合材料方面，都具有吸引力。
发明详述
在一实施方案中，本发明化合物可用下式表示：
其中R1是甲基或乙基基团；R2是二价烃基；X和Y各自独立地为直接键，或醚，酯，酰胺或氨基甲酸酯基团；和Q是二价烃基。
起始的顺丁烯二酰亚胺化合物可以是小分子，如6-顺丁烯二酰亚胺己酸或3-顺丁烯二酰亚胺丙酸，N-(6-羟己基)顺丁烯二酰亚胺，N-(3-羟丙基)顺丁烯二酰亚胺和N-(5-异氰酸根合戊基)顺丁烯二酰亚胺，或者可以是通过将例如6-顺丁烯二酰亚胺己酸或3-顺丁烯二酰亚胺丙酸与双官能团低聚物或聚合物上的一个官能团反应制得的低聚或聚合材料。
无论起始的顺丁烯二酰亚胺化合物是小分子还是低聚或聚合材料，其都含有下式表示的顺丁烯二酰亚胺官能团：
和与起始氧杂环丁烷上第二官能团反应的第二官能团。如上述顺丁烯二酰亚胺起始物除了所述顺丁烯二酰亚胺官能团外还含有羧基，羟基，或异氰酸根官能团。
所述起始氧杂环丁烷化合物可以是小分子或低聚或聚合分子，例如，通过将一种下述小分子氧杂环丁烷起始化合物与双官能团低聚物或聚合物上的一个官能团反应制得。无论在哪种情况下，它都含有一个下列结构式表示的氧杂环丁烷官能团：
和与所述起始顺丁烯二酰亚胺起始化合物上第二官能团起反应的第二官能团。
适合的起始氧杂环丁烷化合物为小分子，包括，例如，
(a)醇，如3—甲基—3—羟甲基氧杂环丁烷，3—乙基—3—羟甲基氧杂环丁烷；
(b)卤化物，如3—甲基—3—溴甲基氧杂环丁烷，3—乙基—3—溴甲基氧杂环丁烷，其可以通过现有技术中已知的方法，用(a)中的一种醇与CBr4反应制得；
(c)烷基卤化物，如3—甲基—3—烷基溴甲基氧杂环丁烷，3—乙基—3—烷基溴甲基氧杂环丁烷，其可以通过现有技术中已知的方法，用烷基二溴化物与一种选自(a)中的氧杂环丁烷醇反应制得；
和(d)甲苯磺酸盐，如3—甲基—3—甲苯磺酰甲基氧杂环丁烷，3—乙基—3—甲苯磺酰甲基氧杂环丁烷，其可以由对甲苯磺酰氯制得：
当所需为含有顺丁烯二酰亚胺和氧杂环丁烷的较长链和分子量较高的化合物时，起始顺丁烯二酰亚胺化合物或起始氧杂环丁烷化合物，或者两者都可以通过与双官能团低聚或聚合材料发生反应而增长。如果第一步反应是在顺丁烯二酰亚胺起始化合物与双官能团低聚或聚合材料之间进行，则该低聚或聚合材料上的第二官能团就必须和氧杂环丁烷起始化合物反应，如果第一步反应是在氧杂环丁烷起始化合物与双官能团低聚或聚合材料之间进行，则该低聚或聚合材料上的第二团能团就必须和顺丁烯二酰亚胺起始化合物反应。合适的市售低聚物和聚合物的例子包括二聚二醇和带有末端羟基官能团的聚丁二烯。
当氧杂环丁烷和顺丁烯二酰亚胺化合物都与双官能团的低聚物或聚合物发生反应增长时，Q可以包括一种由两种低聚或聚合起始物反应得到的官能团，如，醚，酯，氨基甲酸酯或脲官能团。
通常，含有氧杂环丁烷和顺丁烯二酰亚胺官能团的具有创造性的本发明化合物是通过一种含有氧杂环丁烷和第二官能团的起始化合物与一种含有顺丁烯二酰亚胺和与所述氧杂环丁烷化合物上第二官能团起反应的第二官能团的起始化合物一起反应制备的。代表性的反应过程包括已知的加成反应，取代反应和缩合反应。
在另一实施方案中，本发明所述的化合物包括含有多于一个氧杂环丁烷和多于一个顺丁烯二酰亚胺官能团的聚合物。这些化合物由起始的聚合物制备而成，其取决于与起始的氧杂环丁烷化合物和顺丁烯二酰亚胺化合物反应的官能团。
所述聚合物具有如下结构：
其中聚合物表示取决于氧杂环丁烷和顺丁烯二酰亚胺官能团的聚合骨架，m和n是随着人们加入的氧杂环丁烷和顺丁烯二酰亚胺官能团的程度而变化的整数，典型地为2—500，R1是甲基或乙基，R2是二价烃基，和W和Z各自独立地为连接官能团，如醚，羧基，酯，甲基磺酸酯或脲，其是由聚合物上的侧官能团与起始氧杂环丁烷化合物或起始顺丁烯二酰亚胺化合物上的相应的反应性官能团之间的反应而形成的。
聚合物上的侧官能团可以通过例如，含有一到二十个碳原子的烃连接到聚合物骨架上，其本身是附属于所述聚合物骨架。为此，那些附加的部分应被视为聚合物骨架的一部分。
市售的合适的聚合物骨架的例子是具有侧羟基基团的聚丁二烯。所述侧羟基可以与所述含有甲苯磺酰基离去基团的氧杂环丁烷起始化合物和6-顺丁烯二酰亚胺己酸发生反应。此时，连接基团W为醚官能团，Z包含一个酯官能团。
作为另一示例，含有侧羧酸官能团的聚丁二烯可以与所述羟基氧杂环丁烷起始物和所述N-(6-羟己基)顺丁烯二酰亚胺和N-(3-羟丙基)顺丁烯二酰亚胺任一化合物上的羟基官能团发生反应。此时，W和Z基团为酯官能团。当N-(5-异氰酸根合戊基)顺丁烯二酰亚胺与侧羟基反应时，Z基团为酰胺官能团。
聚合起始物可以是市售的，如，购自Zeon Chemicals的丙烯腈—丁二烯橡胶，和购自Johnson Polymer的苯乙烯—丙烯酸共聚物，这些聚合物上的侧官能团是羟基或羧酸官能团。
其他起始的聚合材料可以使用本领域技术人员公知的标准聚合技术由丙烯酸和/或乙烯基单体合成得到。合适的丙烯酸单体包括，α，β—不饱和具有三至五个碳原子的一元或二元羧酸以及丙烯酸酯单体(丙烯酸和甲基丙烯酸烷基酯，其中所述烷基含有一至十四个碳原子)。
例子是，丙烯酸甲酯，甲基丙烯酸甲酯、丙烯酸正辛酯、甲基丙烯酸正壬酯和其相应的支链异构体，如，2-乙基己基丙烯酸酯。合适的乙烯基单体包括乙烯酯、乙烯醚、乙烯卤化物、亚乙烯基卤化物和烯属不饱和烃的腈。例子是醋酸乙烯酯、丙烯酰胺、1—辛基丙烯酰胺、丙烯酸、乙烯基乙醚、氯乙烯、偏氯乙烯、丙烯腈、马来酸酐和苯乙烯。
其它聚合起始物可以使用本领域技术人员公知的标准聚合技术由共轭二烯和/或乙烯基单体制备。合适的共轭二烯单体包括1，3—丁二烯、2—氯—1，3—丁二烯、异戌二烯、1，3—戊二烯和共轭己二烯。合适的乙烯基单体包括苯乙烯、α—甲基苯乙烯、二乙烯基苯、氯乙烯、醋酸乙烯酯、偏二氯乙烯、甲基丙烯酸甲酯、丙烯酸乙酯、乙烯基吡啶、丙烯腈、甲基丙烯腈、甲基丙烯酸、衣康酸和丙烯酸。
本领域技术人员有足够的经验去选择这些单体的合适组合以及随后的能够增加如羟基和羧基官能团的侧官能团反应，用以增加说明书中所述的氧杂环丁烷和顺丁烯二酰亚胺官能团。
实施例
实施例1：乙基氧杂环丁烷顺丁烯二酰亚胺的制备
一个250毫升四口圆底烧瓶，装有机械搅拌器，温度计，氮气吹扫和缓慢滴液漏斗。将6—顺丁烯二酰亚胺己酸(MCA)(25.59克，0.1213摩尔)，3—乙基—3—氧杂环丁烷甲醇(14.10克0.1213摩尔)，4—二甲基氨基吡啶(1.5克，0.0121摩尔)和甲苯(60毫升)加入到烧瓶中，得到含有少量未溶固体的深金黄色溶液。将烧瓶内的物质混和冷却到0—5℃。然后向缓慢滴液漏斗中加入由1，3—二环己基—碳二亚胺(DCC，25.00克，0.1213摩尔)和甲苯(20毫升)制备的溶液。30分钟内将所述DCC/甲苯溶液加入到烧瓶中，同时保持反应温度为10—15℃。
10—15℃下持续搅拌6小时后，薄层色谱(1/1乙酸乙酯/己烷)显示，所述氧杂环丁烷和DCC都已消耗掉。停止反应，从橙红色溶液中过滤出白色固体。再用一体积当量的饱和碳酸氢钠溶液将该反应液洗涤三次。然后从反应中真空除去甲苯，用乙酸乙酯和己烷(1/1体积比)溶液替代。接下来利用柱色谱分离定量的粘度为270cPs的澄清黄色油状物。通过热重分析(TGA)测得所述化合物在200℃时的重量损失为15％。
H1-NMR：δ 6.55(s，2H)，4.55(d，2H)，4.45(d，2H)，4.21(s，2H)，3.41-3.52(t，2H)，2.25-2.42(t，2H)，1.51-1.79(m，4H)，1.11-1.41(m，4H)，0.83-0.95(t，3H)。
实施例2：甲基氧杂环丁烷顺丁烯二酰亚胺的制备
用于制备甲基氧杂环丁烷顺丁烯二酰亚胺的起始物是顺丁烯二酰亚胺己酸氯化物，其结构如下：
通过如下方法制备：
一个500毫升四口圆底烧瓶，配有冷凝器，机械搅拌器，温度计和热油浴。然后加入顺丁烯二酰亚胺己酸(MCA)(40.00克，0.1896摩尔)，二甲基甲酰胺(3滴)和甲苯(125毫升)。将烧瓶中的物质加热到85℃并混和至所有固体溶解为止。随后，将热溶液滗析入一个类似的配有机械搅拌器，鼓泡器，缓慢滴液漏斗和冰浴的烧瓶中。将所述反应液混和并冷却。
保持反应温度为5—10℃通过缓慢滴液漏斗向反应烧瓶中加入草酰氯(36.09克，0.2844摩尔)。随着所述草酰氯的加入，移去冰浴，反应恢复至室温。随着反应温度的升高，鼓泡器显示正在生成气体。将反应持续混和过夜，得到很黑的溶液。然后滗析入一个1升的单口圆底烧瓶中，真空除去甲苯。然后向烧瓶中加入甲苯(200毫升)，脱除三次以降低酸度。所述产物为顺丁烯二酰亚胺氯己酸。
将3—甲基—3—氧杂环丁烷甲醇(19.36克，0.1896摩尔)，三乙胺(19.19克，0.1896摩尔)，4—二甲氨基吡啶(2.32克，0.0190摩尔)和二氯甲烷(175毫升)一起加入到一个配有磁力搅拌棒，缓慢滴液漏斗，干燥管和冰浴的500毫升四口圆底烧瓶中。用氮气吹扫来去除烧瓶中的湿空气。然后将反应液混和冷却至10℃，以足以维持该温度的缓慢速度加入顺丁烯二酰亚胺己酸氯化物(43.4克，0.1896摩尔)的25毫升二氯甲烷溶液。
随着该滴加的进行，将得到的深棕色溶液在室温下混和过夜。薄层色谱(1/1体积比，乙酸乙酯/己烷)显示，基于顺丁烯二酰亚胺氯己酸的消耗，反应进行完全。从反应液中过滤出白色固体，然后用蒸馏水洗涤四次(每次300毫升)。然后通过旋转蒸发从反应液中除去二氯甲烷，用乙酸乙酯/己烷溶液(2/1，分别地，按体积)替代。然后将所述深棕色溶液过硅胶柱进行提纯。然后真空除去溶剂得到澄清的橙色产物，粘度为750cPs。通过热重分析(TGA)测得所述化合物200℃时的重量损失为8％。
H1-NMR：δ 6.65(s，2H)，4.45(d，2H)，4.31(d，2H)，4.06(s，2H)，3.46-3.61(m，2H)，2.31(t，2H)，1.45-1.65(m，4H)，1.16-1.29(m，5H)。
Claims (1)
1.一种化合物，其结构如下：
或
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| US7230055B2 (en) * | 2004-07-29 | 2007-06-12 | National Starch And Chemical Investment Holding Corporation | Compositions containing oxetane compounds for use in semiconductor packaging |
| TWI378091B (en) * | 2006-03-09 | 2012-12-01 | Eisai R&D Man Co Ltd | Multi-cyclic cinnamide derivatives |
| EP2044142A2 (en) * | 2006-06-29 | 2009-04-08 | Medtronic, Inc. | Poly(orthoester) polymers, and methods of making and using same |
| US8324319B2 (en) * | 2007-11-20 | 2012-12-04 | Sridhar Laxmisha M | Redox-induced cationically polymerizable compositions with low cure temperature |
| US8940315B2 (en) * | 2008-04-18 | 2015-01-27 | Medtronic, Inc. | Benzodiazepine formulation in a polyorthoester carrier |
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| US6982338B2 (en) | 2006-01-03 |
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| TW200505908A (en) | 2005-02-16 |
| EP1620430A1 (en) | 2006-02-01 |
| TWI340744B (en) | 2011-04-21 |
| CN1791597A (zh) | 2006-06-21 |
| WO2004101550A1 (en) | 2004-11-25 |
| JP2007502859A (ja) | 2007-02-15 |
| KR20060008975A (ko) | 2006-01-27 |
| JP4907349B2 (ja) | 2012-03-28 |
| US20050209437A1 (en) | 2005-09-22 |
| EP1736473A3 (en) | 2007-01-31 |
| EP1736473A2 (en) | 2006-12-27 |
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