CN113769791B - 一种醇解催化剂的制备方法 - Google Patents
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Abstract
本发明涉及一种醇解催化剂的制备方法，包括如下步骤：步骤A,将5,10,15,20‑四(4‑氨基苯)‑21H,23H‑卟啉和醋酸锌在N2气氛下,在N,N二甲基甲酰胺溶剂中进行反应，反应温度50‑100℃，反应时间1‑2小时；步骤B，通过抽滤去掉N,N二甲基甲酰胺溶剂，获得金属锌卟啉化合物；步骤C,将金属锌卟啉化合物与四醛基四苯乙烯，在邻二甲苯和正丁醇混合溶剂下，在PH范围在3‑5下反应，反应温度100‑130℃，反应2‑3小时得到沉淀物；步骤D,将沉淀物洗涤，得到共价有机化合物Zn‑COFs。本发明能降低反应催化剂用量，并且可以多次循环使用。
Description
技术领域
本发明涉及一种醇解催化剂的制备方法。
背景技术
聚对苯二甲酸乙二醇酯(PET)是由对苯二甲酸(PTA)或对苯二甲酸二甲酯(DMT)和乙二醇缩聚而成的饱和高分子化合物，属于结晶性高聚物，广泛地用于饮料瓶等瓶体中。瓶体用完之后可以进行回收处理，并用于制造纤维、片材、非食品包装用瓶和不饱和聚酯树脂。
现有技术中，一种处理方法是采用醇解进行瓶体回收，将PET瓶片、二甘醇、抗氧剂以及催化剂投入反应瓶中，升温进行醇解反应。催化剂一般采用氯化亚锡或者醋酸锌。现有的催化剂用于PET醇解反应，醇解反应的时间相对较长，醇解温度相对较高，并且目前主流的锡类催化剂具有一定的毒性，此外催化剂不易进行回收利用，整体而言，使得PET醇解反应的材料和能耗相对较大。
鉴于此，本案发明人对上述问题进行深入研究，遂有本案产生。
发明内容
本发明的目的在于提供一种能够降低醇解时间、减少催化剂用量醇解催化剂的制备方法。
为了达到上述目的，本发明采用这样的技术方案：
一种醇解催化剂的制备方法，其特征在于，包括如下步骤：
步骤A,将5,10,15,20-四(4-氨基苯)-21H,23H-卟啉和醋酸锌在N2气氛下,在N,N二甲基甲酰胺溶剂中进行反应，反应温度50-100℃，反应时间1-2小时；
步骤B，通过抽滤去掉N,N二甲基甲酰胺溶剂，然后用蒸馏水洗去未反应的醋酸锌,烘干后，获得金属锌卟啉化合物；
步骤C,将金属锌卟啉化合物与四醛基四苯乙烯，在邻二甲苯和正丁醇混合溶剂下，在PH范围在3-5下反应，反应温度100-130℃，反应2-3小时得到沉淀物；
步骤D,将沉淀物洗涤，干燥后,得到共价有机化合物Zn-COFs。
在上述方案中，所述5,10,15,20-四(4-氨基苯)-21H,23H-卟啉和所述醋酸锌的摩尔比为1:1.05-1.2。
在上述方案中，所述金属锌卟啉化合物与所述四醛基四苯乙烯的摩尔比为1:1.1-1.2。
在上述方案中，所述混合溶剂中，所述邻二甲苯和所述正丁醇的体积比为1:1。
采用本发明的技术方案，通过合成金属锌卟啉后与四醛基四苯乙烯通过溶剂热合成多孔有机共价化合物Zn-COFs，锌配位在卟啉环中提升催化效果，并且金属锌负载在高比表面积的多孔材料上，催化活性位点增加，提高催化效果。比直接用醋酸锌效果改善很大，同等条件下，直接用醋酸锌比例1.5‰，温度210℃，反应完全需时间7小时，醇解酸值为9.7，放置24小时发生分层，醇解不充分。本发明的催化剂活性提升，在210℃时表现出优异的催化性能，催化剂比例为0.5‰，缩短反应时间至3小时仍表现出良好的催化性能，并且可以多次循环使用，催化活性并无明显较弱。
附图说明
图1为本发明中有机共价化合物Zn-COFs的XRD粉末衍射图。
图2为本发明中有机共价化合物Zn-COFs多孔晶体结构示意图。
图3为本发明中有机共价化合物Zn-COFs的N2等温吸附脱附曲线。
具体实施方式
为了进一步解释本发明的技术方案，下面结合实施例进行详细阐述。
实施例1
将5,10,15,20-四(4-氨基苯)-21H,23H-卟啉(该化合物的CAS号是：22112-84-1)67.5克，醋酸锌19.21克，N,N二甲基甲酰胺(即DMF)溶剂200ml投入圆底四口反应瓶中，反应温度50℃，反应时间2小时，反应完毕后，通过减压抽滤去掉溶剂DMF，然后用蒸馏水洗去未反应的醋酸锌。烘箱干燥即可，烘箱温度为100℃。将获得的金属锌卟啉化合物ZnII-TAP与四醛基四苯乙烯(该化合物CAS：2170454-48-4)进行胺醛缩合反应，反应摩尔比1:1.1，在混合溶剂(邻二甲苯和正丁醇各100ml)，PH值为3.0的酸性(酸性可以稀盐酸或醋酸调节)条件下，通过反应温度100℃，反应时间3小时得到沉淀物，将溶剂过滤掉，用丙酮和蒸馏水洗涤，烘箱干燥，烘箱温度为100℃，通过XRD粉末衍射测试未得到明显的晶态结构信息。
实施例2
将5,10,15,20-四(4-氨基苯)-21H,23H-卟啉67.5克，醋酸锌21.04克，DMF溶剂200ml投入圆底四口反应瓶中，反应温度80℃，反应时间2小时，反应完毕后，通过减压抽滤去掉溶剂DMF，然后用蒸馏水洗去未反应的醋酸锌。烘箱干燥即可，烘箱温度为100℃。将获得的金属锌卟啉化合物ZnII-TAP与四醛基四苯乙烯(TPE)进行胺醛缩合反应，反应摩尔比1:1.1，在混合溶剂(邻二甲苯和正丁醇各100ml)，PH值为3.0的酸性条件下，反应温度130℃，反应时间3小时得到沉淀物，将溶剂过滤掉，用丙酮和蒸馏水洗涤，烘箱干燥，烘箱温度为100℃，通过XRD粉末衍射测试未得到明显的晶态结构信息。
实施例3
将5,10,15,20-四(4-氨基苯)-21H,23H-卟啉67.5克，醋酸锌21.96克，DMF溶剂200ml投入圆底四口反应瓶中，反应温度100℃，反应时间2小时，反应完毕后，通过减压抽滤去掉溶剂DMF，然后用蒸馏水洗去未反应的醋酸锌。烘箱干燥即可，烘箱温度为100℃。将获得的金属锌卟啉化合物ZnII-TAP与四醛基四苯乙烯(TPE)进行胺醛缩合反应，反应摩尔比1:1.1，在混合溶剂(邻二甲苯和正丁醇各100ml)，PH值为4.5的酸性条件下，反应温度130℃，反应时间3小时得到沉淀物，将溶剂过滤掉，用丙酮和蒸馏水洗涤，烘箱干燥，通过XRD粉末衍射测试得到明显的晶态结构信息，并且进行氮气吸脱附测试，理论计算出其比表面积。图1为Zn-COFs的X-射线粉末衍射图，表明该化合物具有(110)晶面的四方点阵结构，图2为该化合物的多孔晶体结构示意图，图3是该化合物的氮气吸脱附测试曲线，图中可知该化合物每克吸附氮气为390cm3，具有很好的气体吸附性能和多孔结构，理论计算比表面积达到968m2/g。因此，该化合物具有的多孔结构和高的比表面积为其催化性能提供了有利的条件。图1中，横坐标为衍射2θ角/度，图3中，纵坐标表示氮气吸附(单位为立方厘米/克)，横坐标表示相对压力((即吸附质压力P与其饱和蒸气压P0之比)。
实施例4
将1000克PET，800克二甘醇，2克抗氧剂三苯酯(也即亚磷酸三苯酯，下同)和催化剂氯化亚锡(催化剂的添加比例为1.5‰，以PET量计)依次投入反应瓶中，逐步升温进行醇解反应，反应温度210℃，反应时间需7小时，反应完毕后测试酸值为5.5mgKOH/g(酸值＜6.0mgKOH/g)，反应溶液清澈透明，放置24小时不分层。
实施例5
将1000克PET，800克二甘醇，2克抗氧剂三苯酯和催化剂醋酸锌(催化剂的添加比例为1.5‰，以PET量计)依次投入反应瓶中，逐步升温进行醇解反应，反应温度210℃，反应时间需7小时，反应完毕后测试酸值为9.7mgKOH/g，酸值高，放置24小时分层，醇解不充分，需要提高醇解温度至230℃，氧化严重颜色黄。
实施例6
将1000克PET，800克二甘醇，2克抗氧剂三苯酯和本发明的催化剂(采用实施例1中制得的催化剂，下同，催化剂的添加比例为1.5‰，以PET量计)依次投入反应瓶中，逐步升温进行醇解反应，反应温度210℃，反应时间7小时，反应完毕后测试酸值为4.8mgKOH/g，醇解效果好，醇解完毕后可以简单过滤，多次循环使用。
实施例7
将1000克PET，800克二甘醇，2克抗氧剂三苯酯和本发明的催化剂(催化剂的添加比例为1.5‰，以PET量计)依次投入反应瓶中，，逐步升温进行醇解反应，反应温度210℃，反应时间3小时，反应完毕后测试酸值为5.0mgKOH/g，醇解效果好，不分层。
实施例8
将1000克PET，800克二甘醇，2克抗氧剂三苯酯和本发明的催化剂(催化剂的添加比例为0.5‰，以PET量计，)依次投入反应瓶中，逐步升温进行醇解反应，反应温度210℃，反应时间3小时，反应完毕后测试酸值为5.2mgKOH/g,醇解效果好，不分层。同等催化剂用量和使用条件下，本发明的催化剂经过10次循环使用后,反应测试酸值为5.8mgKOH/g，醇解效果无明显减弱。
三种催化剂应用在醇解工艺中，效果对比如下表：
本发明的产品形式并非限于本案实施例，任何人对其进行类似思路的适当变化或修饰，皆应视为不脱离本发明的专利范畴。
Claims (4)
1.一种醇解催化剂的制备方法，其特征在于，包括如下步骤：
步骤A,将5,10,15,20-四(4-氨基苯)-21H,23H-卟啉和醋酸锌在N2气氛下,在N,N二甲基甲酰胺溶剂中进行反应，反应温度50-100℃，反应时间1-2小时；
步骤B，通过抽滤去掉N,N二甲基甲酰胺溶剂，然后用蒸馏水洗去未反应的醋酸锌,烘干后，获得金属锌卟啉化合物；
步骤C,将金属锌卟啉化合物与四醛基四苯乙烯，在邻二甲苯和正丁醇混合溶剂下，在PH范围在3-5下反应，反应温度100-130℃，反应2-3小时得到沉淀物；
步骤D,将沉淀物洗涤，干燥后,得到共价有机化合物Zn-COFs。
2.如权利要求1所述的一种醇解催化剂的制备方法，其特征在于：所述5,10,15,20-四(4-氨基苯)-21H,23H-卟啉和所述醋酸锌的摩尔比为1:1.05-1.2。
3.如权利要求2所述的一种醇解催化剂的制备方法，其特征在于：所述金属锌卟啉化合物与所述四醛基四苯乙烯的摩尔比为1:1.1-1.2。
4.如权利要求3所述的一种醇解催化剂的制备方法，其特征在于：所述混合溶剂中，所述邻二甲苯和所述正丁醇的体积比为1:1。
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