CN114874250B - 一种吡啶基含n配位的双金属铝配合物及制备方法和应用 - Google Patents
一种吡啶基含n配位的双金属铝配合物及制备方法和应用 Download PDFInfo
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 18
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- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 6
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- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
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Abstract
本发明公开了一种吡啶基含N配位的双金属铝配合物及制备方法和应用，属于配合物技术领域。涉及ε‑己内酯开环聚合反应，具体是一种以吡啶基肼化合物为配体的双金属铝催化剂。在氮气氛围中，以甲苯为反应溶剂，双吡啶基配体1,2‑二(3,3‑二甲基‑1‑(2‑吡啶基)丁烷‑2‑亚基)肼与三甲基铝反应，加热搅拌，冷却至室温，过滤，真空条件下浓缩滤液，低温下析出无色透明晶体，即为双吡啶基金属铝配合物。该催化剂制备的过程简单且产率高，无需引发剂就能催化ε‑己内酯的开环聚合，得到性能优良的聚合物。
Description
技术领域
本发明涉及有机金属配合物催化剂制备技术领域，具体涉及一种吡啶基含N配位的双金属铝配合物及制备方法和应用。
背景技术
近年来由于化石原料的枯竭，开发可生物降解的高分子生物材料以取代不可降解的传统塑料已成为全球科学家研究的热点。在各种已知的可生物降解聚合物中，线性脂肪族聚酯(如：聚己内酯和聚丙交酯)占有突出的地位，其水解或酶解链会产生羟基酸，在大多数情况下，这些羟基酸最终会被代谢掉。聚ε-己内酯(PCL)有优良的生物相容性、无毒性、生物可降解性等，被广泛地应用在各个领域，如：一次性薄膜、手术缝合线以及药物缓释系统等方面。
聚酯通常由二醇和二元酸的缩聚反应或环酯的开环聚合(ROP)产生。然而直接缩聚法得到聚合物分子量低，易分解。获得脂肪族聚酯最方便和高效的方法是环酯开环聚合，该方法可以避免副产物对聚合反应的影响，主要反应机理包括阴离子、阳离子、配位插入和有机催化。
金属配合物催化剂是合成脂肪族聚酯材料使用最为广泛的催化剂，目前已经有碱金属、碱土金属、稀土金属、过渡金属以及铝、镓等金属配合物被证实可以催化环酯开环聚合。然而由于部分金属催化剂容易残存于聚合物材料中，可能使得聚合材料存在一定的生物毒性，大大降低了其使用范围。因此，开发具有低毒性的铝配合物催化剂是解决该类问题的方法之一，尤其是高活性的双金属铝配合物催化剂备受青睐。
发明内容
针对目前合成聚己内酯的催化剂具有生物毒性，催化聚合过程需要添加引发剂，金属铝配合物的催化活性低的问题，本发明提供了一种吡啶基含N配位的双金属铝配合物及制备方法和应用。
本发明的目的在于提供一种吡啶基含N配位的双金属铝配合物及其合成方法和应用。该方法操作简单，作为催化剂的催化活性高，且催化ε-己内酯开环聚合不需要添加其他引发剂。
为了达到上述目的，本发明采用了下列技术方案：
一种吡啶基含N配位的双金属铝配合物，所述吡啶基含N配位的双金属铝配合物的结构式为：
所述吡啶基含N配位的双金属铝配合物的晶体属于三斜晶系，P-1空间群，晶胞参数为：α＝86.286(13)°，β＝70.866(13)°，γ＝63.100(15)°。
吡啶基含N配位的双金属铝配合物的制备方法，包括以下步骤：在氮气氛围中，以甲苯为反应溶剂，双吡啶基配体1,2-二(3,3-二甲基-1-(2-吡啶基)丁烷-2-亚基)肼与三甲基铝进行加热反应，搅拌冷却至室温，过滤，真空条件下浓缩滤液，低温下析出无色透明晶体，即为吡啶基含N配位的双金属铝配合物。
进一步，所述双吡啶基配体与三甲基铝的摩尔比为2:1～2.2:1。
进一步，所述加热反应的温度为110℃～120℃，反应时间为10～12h。
进一步，所述低温的温度为-20℃～0℃。
吡啶基含N配位的双金属铝配合物在催化ε-己内酯聚合反应中的应用。
吡啶基含N配位的双金属铝配合物的应用，在催化ε-己内酯聚合反应中作为催化剂。
上述吡啶基含N配位的双金属铝配合物的应用，在Schlenk反应瓶中，加入0.025g吡啶基含N配位的双金属铝配合物，加入5mL甲苯溶解，在特定温度下，通过注射器加入不同摩尔量的ε-己内酯，反应至固定时间后取样，加入猝灭剂，然后加入大量甲醇使聚合物析出，过滤，再用甲醇洗涤数次后过中性氧化铝短柱，真空干燥，得到聚ε-己内酯。
进一步，所述猝灭剂为体积比95％甲醇和5％HCl。
进一步，所述ε-己内酯与双吡啶基铝配合物的摩尔比例为100:1～800:1。
与现有技术相比本发明具有以下优点：
本发明合成的金属配合物催化剂为双金属中心配合物催化剂，制备方法简单，条件要求低，且产率高。该催化剂具有毒性小，生物相容性良好和催化活性高等特点，可得到性能良好的聚酯材料。相比于同类型单金属中心催化剂其催化活性更高，且不需要引发剂就可催化ε-己内酯开环聚合。
附图说明
图1本发明中吡啶基含N配位的双铝金属催化剂的晶体结构图。
具体实施方式
实施例1吡啶基含N配位的双金属铝催化剂的合成
在氮气氛围下，以甲苯为反应溶剂，向1,2-二(3,3-二甲基-1-(2-吡啶基)丁烷-2-亚基)肼(0.350g，1.00mmol)的甲苯溶液中缓慢滴加2倍摩尔量的三甲基铝溶液(2.00mL，1.0M的正己烷溶液)，搅拌在120℃下反应12h，冷却至室温，过滤，真空浓缩滤液，在-20℃放置2d后析出无色透明晶体，即为吡啶基含N配位的双铝金属催化剂，0.38g，产率为77％。
实施例2吡啶基含N配位的双金属铝催化剂的合成
在氮气氛围下，以甲苯为反应溶剂，向1,2-二(3,3-二甲基-1-(2-吡啶基)丁烷-2-亚基)肼(0.350g，1.00mmol)的甲苯溶液中缓慢滴加2.2倍摩尔量的三甲基铝溶液(2.20mL，1.0M的正己烷溶液)，滴加完毕后在110℃下搅拌反应10h，冷却至室温，过滤，真空浓缩滤液，在0℃放置3d后析出无色透明晶体，即为吡啶基含N配位的双铝金属催化剂，0.35g，产率为71％。
上述实施例所得的产品的核磁测试结果相同，具体见下述：
1H NMR(600MHz,Chloroform-d)δ8.62(s,2H),7.72(s,2H),7.24(s,2H),7.04(s,2H),4.09(s,4H),0.84(s,18H),-0.78(s,12H),-0.90(s,6H)。13C NMR(151MHz,Benzene-d6)δ158.50,148.40,121.84,50.78,39.18,35.87,27.75,-5.82。
实施例3吡啶基含N配位的双金属铝配合物的结构测定
选取大小合适的晶体，在室温条件下使用Bruker Apex II CCD衍射仪收集晶体数据，石墨单色器Mo-Kα作为辐射光源。使用SMART软件确定晶胞参数，通过SADABS程序进行吸收校正。晶体结构使用SHELXS-2014程序采用直接法解出，并采用全矩阵最小二乘法基于F2进行精修，理论加氢确定所有H原子位置。晶体结构见图1，晶体学测定数据见表1。
表1双金属铝配合物的晶体学数据
部分键长Al(1)-C(12)1.978(3)，Al(1)-C(13)1.961(4)，Al(1)-C(14)1.978(3)，Al(1)-N(1)2.049(2)，N(2)-N(3)1.410(3)；部分键角(°)：C(13)-Al(1)-N(1)104.88(14)，C(14)-Al(1)-N(1)104.24(10)，C(12)-Al(1)-N(1)105.46(11)。
实施例4吡啶基含N配位的双金属铝配合物催化ε-己内酯开环聚合
以实施例1中的双吡啶基铝配合物为催化剂，ε-己内酯为底物，进行开环聚合反应条件筛选。反应一般步骤为：在Schlenk反应瓶中，加入0.025g吡啶基含N配位的双金属铝配合物，加入5mL甲苯溶解，在特定温度下，通过注射器加入不同摩尔量的ε-己内酯，溶液开始变得粘稠。反应至固定时间后取样，加入猝灭剂(95％甲醇+5％HCl)，然后加入大量甲醇使聚合物析出，过滤，用甲醇再洗涤数次后过中性氧化铝短柱，真空干燥，得聚ε-己内酯。
表2吡啶基含N配位的双金属铝配合物催化ε-己内酯开环聚合a
其中，a表示反应条件：ε-己内酯浓度为1.0mol/L，通过盐酸的甲醇溶液(0.6mol/L)进行猝灭。b表示转化率通过核磁氢谱进行测定。c表示分子量及分子量分布通过GPC测定。
总之，吡啶基含N配位的双金属铝催化剂，制备方法简单，产率高，催化效率较高，相比于大部分金属铝配合物催化剂不需要加引发剂就能够催化ε-己内酯开环聚合。
本发明说明书中未作详细描述的内容属于本领域专业技术人员公知的现有技术。尽管上面对本发明说明性的具体实施方式进行了描述，以便于本技术领的技术人员理解本发明，但应该清楚，本发明不限于具体实施方式的范围，对本技术领域的普通技术人员来讲，只要各种变化在所附的权利要求限定和确定的本发明的精神和范围内，这些变化是显而易见的，一切利用本发明构思的发明创造均在保护之列。
Claims (10)
1.一种吡啶基含N配位的双金属铝配合物，其特征在于：所述吡啶基含N配位的双金属铝配合物的结构式为：
所述吡啶基含N配位的双金属铝配合物的晶体属于三斜晶系，P-1空间群，晶胞参数为：α＝86.286(13)°，β＝70.866(13)°，γ＝63.100(15)°。
2.根据权利要求1所述的吡啶基含N配位的双金属铝配合物的制备方法，其特征在于：包括以下步骤：在氮气氛围中，以甲苯为反应溶剂，双吡啶基配体1,2-二(3,3-二甲基-1-(2-吡啶基)丁烷-2-亚基)肼与三甲基铝进行加热反应，搅拌冷却至室温，过滤，真空条件下浓缩滤液，低温下析出无色透明晶体，即为吡啶基含N配位的双金属铝配合物。
3.根据权利要求2所述的吡啶基含N配位的双金属铝配合物的制备方法，其特征在于：所述双吡啶基配体与三甲基铝的摩尔比为2:1～2.2:1。
4.根据权利要求2所述的吡啶基含N配位的双金属铝配合物的制备方法，其特征在于：所述加热反应的温度为110℃～120℃，反应时间为10h～12h。
5.根据权利要求2所述的吡啶基含N配位的双金属铝配合物的制备方法，其特征在于：所述低温的温度为-20℃～0℃。
6.根据权利要求1所述的吡啶基含N配位的双金属铝配合物在催化ε-己内酯聚合反应中的应用。
7.根据权利要求6所述的吡啶基含N配位的双金属铝配合物的应用，其特征在于：在催化ε-己内酯聚合反应中作为催化剂。
8.根据权利要求6或7任意一项所述的吡啶基含N配位的双金属铝配合物的应用，其特征在于：在Schlenk反应瓶中，加入0.025g吡啶基含N配位的双金属铝配合物，加入5mL甲苯溶解，在特定温度下，通过注射器加入不同摩尔量的ε-己内酯，反应至固定时间后取样，加入猝灭剂，然后加入大量甲醇使聚合物析出，过滤，再用甲醇洗涤数次后过中性氧化铝短柱，真空干燥，得到聚ε-己内酯。
9.根据权利要求8所述的吡啶基含N配位的双金属铝配合物的应用，其特征在于：所述猝灭剂为体积比95％甲醇和5％HCl。
10.根据权利要求8所述的吡啶基含N配位的双金属铝配合物的应用，其特征在于：所述ε-己内酯与吡啶基含N配位的双金属铝配合物的摩尔比例为100:1～800:1。
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| WO2013128175A1 (en) * | 2012-02-27 | 2013-09-06 | The University Court Of The University Of Edinburgh | Aluminum salen and salan catalysts for ring-opening polymerisation of cyclic esters |
| CN104926716A (zh) * | 2015-06-10 | 2015-09-23 | 哈尔滨工业大学 | 吡啶衍生物2,6-二[(6-甲氧基吡啶-2-基)甲基]吡啶及其合成方法 |
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