CN102250131B - β-酮二亚胺基二烷氧基铝配合物和其制备方法及其在ε-己内酯开环聚合中的应用 - Google Patents

β-酮二亚胺基二烷氧基铝配合物和其制备方法及其在ε-己内酯开环聚合中的应用 Download PDF

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CN102250131B
CN102250131B CN201010178007.4A CN201010178007A CN102250131B CN 102250131 B CN102250131 B CN 102250131B CN 201010178007 A CN201010178007 A CN 201010178007A CN 102250131 B CN102250131 B CN 102250131B
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郝海军
杰瑞T·头
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Beijing University of Chemical Technology
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Abstract

β-酮二亚胺基二烷氧基铝配合物和其制备方法及其在ε-己内酯开环聚合中的应用，属于金属有机化合物的合成和催化技术领域。本发明涉及β-酮二亚胺基二烷氧基铝配合物。本发明还涉及到这些化合物的制备方法。该化合物具有制备简单、活性高且能控制聚合物分布在较窄的范围内的特点。

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β-酮二亚胺基二烷氧基铝配合物和其制备方法及其在ε-己内酯开环聚合中的应用
技术领域：
本发明属于金属有机化合物的合成和催化技术领域，β-酮二亚胺基二烷氧基铝配合物和其制备方法及其在ε-己内酯开环聚合中的应用。
背景技术：
聚乳酸和聚ε-己内酯是可生物降解、可生物吸收的高分子材料，易于与其它高分子材料共混制备，可改善高分子材料的可降解性。
2008年，曾有报道，β-酮二亚胺基二烷基铝化合物可催化ε-己内酯的开环聚合反应，虽有一定的反应活性，但所得聚己内酯的分子量分布较宽。增加β-酮二亚胺配体的位阻，反应活性又会降低。作者试图从β-酮二亚胺基二氯化铝化合物同烷基钠反应来制备β-酮二亚胺基二烷基铝化合物没有成功。我们认为，要想控制分子量分布处于较窄的范围内，必须增加β-酮二亚胺配位的位阻，而二烷氧可以增加铝的路易斯酸性从而提供反应的活性。
本发明合成这类位阻大的β-酮二亚胺基二烷氧基铝配合物，并发明了一种简单的制备方法，并将其用作ε-己内酯开环聚合中的引发剂。所得聚合物的具有分子量分布窄的特点。
发明内容：
本发明的目的在于提供一类新化合物：β-酮二亚胺基二烷氧基铝配合物。
本发明的目的在于提供β-酮二亚胺基二烷氧基铝配合物的制备方法。
本发明还提供了上述配合物在ε-己内酯合成中的应用。
本发明所提供的β-酮亚胺三齿铝配合物具体结构如下：
Figure GSA00000122630100011
式中，R为甲基或乙基或苄基；Ar为2，6-二异丙基苯基。
上述化合物可具有如下结构的β-酮二亚胺基铝二氢化合物II通过与甲醇、乙醇或苄醇反应来制备。
Figure GSA00000122630100021
上述结构中式中，Ar为2，6-二异丙基苯基。
本发明合成的β-酮二亚胺基二烷氧基铝配合物可以用作催化剂，推荐用于ε-己内酯的开环聚合。例如在甲苯、四氢呋喃、二氯甲烷溶液中，与60-120℃条件下催化ε-己内酯的开环聚合。
具体实施方式：
通过下述实施实例将有助于进一步理解本发明，但并不能限制本发明的内容。
实施例1：
在100ml的Schlenk瓶中加入铝的二氢化合物CH(CMeNAr)2AlH2(1.09g，2.44mmol)，加入30ml甲苯溶解。在氮气保护下，用注射器往Schlenk瓶中加入蒸馏过的苄醇(0.53g，4.88mmol)。该反应体系在室温下搅拌36h，真空下除去所有挥发性物质，在得到的固体中加入30ml正己烷，加热至40℃使其完全溶解，放置0℃结晶，得到无色晶体化合物1。收率62％。熔点：128-130℃。元素分析值C43H55AlN2O2，C＝78.31％，H＝8.35％，N＝4.25％，1H NMR(600MHz，CDCl3)5.276(s 1H：γ-CH)，3.302(sept，4H，CHMe2)，1.852(s，6H，Me)，1.013(d，12H，CHMe3)，1.105(d，12H，CHMe3)，4.594(s，4H，OCH2Ph)，7.383(m，15H，Ph)。
实施例2：
在100ml的Schlenk瓶中加入铝的二氢化合物CH(CMeNAr)2AlH2(1.0g，2.24mmol)，加入30ml甲苯溶解。在氮气保护下，用注射器往Schlenk瓶中加入蒸馏过的甲醇(0.14g，4.88mmol)。该反应体系在室温下搅拌24h，真空下除去所有挥发性物质，在得到的固体中加入20ml正己烷使其溶解。在0℃静置24h后，将得到的固体过滤，在-20℃下静置48h，得到无色晶体化合物2。收率49％。熔点：152-154℃。元素分析值C31H47AlN2O2；，C，73.42％；H，9.28％；N.5.53％.1H NMR(600MHz，CDCl3)5.176(s 1H：γ-CH)，3.296(sept，4H，CHMe2)，1.769(s，6H，Me)，1.318(d，12H，CHMe3)，1.306(d，12H，CHMe3)，3.296(s，6H，OMe)，7.280(m，6H，Ph)。
实施例3：
在氮气保护下，将适量0.01M新制的化合物2的甲苯溶液加入到10ml干燥的甲苯中作为引发剂，然后在氮气保护下用密封性好的针管加入ε-己内酯与催化剂摩尔比为1000∶1，使体系在室温下反应8h，减压除去甲苯，然后加入5ml THF，搅拌下加入1ml乙酸淬灭反应，加入30ml己烷搅拌使聚合物沉淀出来，聚合物经过滤分离、室温真空干燥后用GPC进行表征，转化率为92％，测得数均分子量103965，分子量分布1.08。

Claims (6)

1.一种β-酮二亚胺基铝二烷氧基化合物，其特征在于，具有如下通式I的结构，
Figure FSB0000119931450000011
式中，R为甲基或乙基；Ar为2,6-二异丙基苯基。 
2.一种权利要求1所述的β-酮二亚胺基铝二烷氧基化合物的制备方法，其特征在于其经由β-酮二亚胺基铝二氢化合物通过与二倍摩尔当量的醇进行醇解反应来制备，其中，β-酮二亚胺基铝二氢化合物具有如下确定的结构式II： 
Figure FSB0000119931450000012
式中，Ar为2,6-二异丙基苯基。 
3.根据权利要求2所述的方法，其特征在于，进行醇解反应所选用的醇为甲醇或乙醇。 
4.根据权利要求2所述的方法，其特征在于，进行醇解反应所选用的有机溶剂选自苯或甲苯或正己烷或环己烷或四氢呋喃或乙醚。 
5.根据权利要求2所述的方法，进行醇解反应的温度为-78℃至100℃。 
6.根据权利要求1所述的β-酮二亚胺基铝二烷氧基化合物的应用，其特征在于，用作ε-己内酯的开环聚合反应的催化剂，所选用的反应溶剂选自甲苯或四氢呋喃或二氯甲烷，反应在60-120℃条件下进行，在无溶剂条件下此反应在130℃下进行。 
CN201010178007.4A 2010-05-20 2010-05-20 β-酮二亚胺基二烷氧基铝配合物和其制备方法及其在ε-己内酯开环聚合中的应用 Expired - Fee Related CN102250131B (zh)

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李良钊等.席夫碱铝双核配合物的合成及其对ε-己内酯的催化作用.《应用化学》.2007,第24卷(第8期),第878-882页.

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