CN107456956B - 聚酯高分子/黏土复合吸附材料制法及其产品和应用 - Google Patents
聚酯高分子/黏土复合吸附材料制法及其产品和应用 Download PDFInfo
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Abstract
本发明公开了一种聚酯高分子/黏土复合吸附材料制法及其产品和应用，包括黏土的阳离子交换和原位插层聚合，其特点是在阳离子交换和复合反应之前都对原料进行了湿法研磨工艺处理，得到均一分散的浆料，使得阳离子交换能够充分进行，同时保证原位聚合反应中填料组分能免于团聚且均匀分散于聚酯基材中，最后得到的聚酯复合吸附材料在能够有效吸附有机污染物的同时，负载于黏土上的铜离子和锌离子还能达到防霉和抗菌的效果，石墨烯则起防腐作用，从而大大提到了聚合物/黏土复合吸附材料对水环境的适应性。
Description
技术领域
本发明属于高分子复合材料制备领域，具体涉及一种聚酯高分子/黏土复合吸附材料制法及其产品和应用。
背景技术
水污染是当前社会非常关注的一个问题，近些年来随着经济转型压力的增大，政府和社会对经济的产出不再单纯关注GDP指标，对增长的质量要求也越来越重视。工业生产中或多或少都会有不同程度的废水排放，环保部门制订了严格的规章来规范企业，执法力度也更强。不仅工矿企业需要对生产废水进行达标处理，公共水域也会因为各种因素的影响出现一些局部水污染事件，其中有机物污染是众所周知很重要的一部分，各方都在努力加强治理技术的升级换代。
天然黏土矿物中存在大量可交换的亲水性阳离子，使黏土表面通常吸附一层薄的水膜，会使层间距逐步扩大，因而不断吸附周围物质形成絮凝复合物。利用这种特性制备阳离子插层聚合物，可以有效吸附疏水性有机污染物。
发明内容
为克服现有技术的不足，本发明目的在于：提供一种聚酯高分子/黏土复合吸附材料的制备方法。
本发明的再一目的在于：提供上述制备方法获得的聚酯高分子/黏土复合吸附材料产品。
本发明的又一目的在于：提供所述聚酯高分子/黏土复合吸附材料的应用。
本发明目的通过下述方案实现：一种聚酯高分子/黏土复合吸附材料的制备方法，包括如下步骤：
(1)黏土的阳离子交换:取黏土100g、四水甲酸铜(C2H2CuO4) 21～35g、醋酸锌(C4H10O6Zn) 20～34g和去离子水200～400ml配料，经过预混后灌入湿法研磨设备，研磨介质为氧化锆微球，研磨转速1700～2000rpm，研磨期间物料温度控制在20℃以下，当物料中颗粒粒径D90=2μm时出料，然后在高速剪切机中进行黏土的阳离子交换反应，反应温度65~70℃，剪切速度20000~30000rpm，反应时间24～36小时，得到浆料A；
(2)原位插层聚合:在浆料A中加入2777～8333g对苯二甲酸(C8H6O4),1342～4027g乙二醇(C2H6O2)，0.83～2.49g氧化锑(Sb2O3)，0.09～0.27g四水合乙酸钴(C4H14CoO8)，46.7～140μl磷酸三甲酯(C3H9O4P)，50～100g石墨烯粉末，预搅拌后进行湿法研磨，研磨介质为氧化锆微球，研磨转速1700～2000rpm，研磨期间物料温度控制在20～30℃，当物料中颗粒粒径D90=2μm时出料并移入聚合反应釜，边搅拌边升温至120℃，抽真空脱水并用N2吹扫至不再收集到凝结水，升温至225～260℃开始缩聚脱水，在保证釜压安全的前提下释放水蒸气至不再收集到凝结水，升温至270～280℃，抽乙二醇至真空度低于90Pa以下，放料，得到聚酯高分子/黏土复合吸附材料。
本发明提供了一种聚酯高分子/黏土复合材料的制备方法，采用阳离子交换法对天然黏土进行功能性处理，然后采用原位聚合工艺将黏土等填料均匀复合到聚酯中，从而得到具有防霉抗菌防腐效果的聚酯/黏土复合吸附材料。本本发明主要原理是利用天然黏土的层间结构，使用铜盐和锌盐对其进行阳离子交换，然后和聚酯进行复合制成聚合物黏土复合吸附材料。
所用黏土为提纯过的蒙脱石(MMT)。
湿法研磨所用磨介氧化锆微球直径≤0.2mm。
本发明提供一种上述制备方法得到的聚酯高分子/黏土复合吸附材料。
本发明还提供一种上述制备方法得到的聚酯高分子/黏土复合吸附材在污水有机物吸附的应用。
本发明的优越性在于：在阳离子交换和复合反应之前都对原料进行了湿法研磨工艺处理，得到均一分散的浆料，使得阳离子交换能够充分进行，同时保证原位聚合反应中填料组分能免于团聚且均匀分散于聚酯基材中，最后得到的聚酯复合吸附材料在能够有效吸附有机污染物的同时，负载于黏土上的铜离子和锌离子还能达到防霉和抗菌的效果，石墨烯则起防腐作用，从而大大提到了聚合物/黏土复合吸附材料对水环境的适应性。
具体实施方式
本发明通过下面的具体实例进行详细描述，但本发明的保护范围不受限于这些实施例。
实施例1：
(1)黏土的阳离子交换:取黏土100g、四水甲酸铜(C2H2CuO4)21g、醋酸锌(C4H10O6Zn)34g和去离子水200ml配料，经过预混后灌入湿法研磨设备，研磨介质为氧化锆微球，研磨转速1700rpm，研磨期间物料温度控制在20℃以下，当物料中颗粒粒径D90=2μm时出料，然后在高速剪切机中进行黏土的阳离子交换反应，反应温度65℃，剪切速度20000rpm，反应时间36小时，得到浆料A。
(2)原位插层聚合:在浆料A中加入2777g对苯二甲酸(C8H6O4)，1342g乙二醇(C2H6O2)，0.83g氧化锑(Sb2O3)，0.09g四水合乙酸钴(C4H14CoO8)，46.7μl磷酸三甲酯(C3H9O4P)，50g石墨烯粉末，预搅拌后进行湿法研磨，研磨介质为氧化锆微球，研磨转速1700rpm，研磨期间物料温度控制在30℃，当物料中颗粒粒径D90=2μm时出料并移入聚合反应釜，边搅拌边升温至120℃，抽真空脱水并用N2吹扫至不再收集到凝结水，升温至250℃开始缩聚脱水，在保证釜压安全的前提下释放水蒸气至不再收集到凝结水，升温至280℃，抽乙二醇至真空度低于90Pa以下，放料，得到聚酯复合吸附材料。
实施例2：
(1)黏土的阳离子交换:取黏土100g、四水甲酸铜(C2H2CuO4)35g、醋酸锌(C4H10O6Zn) 20g和去离子水400ml配料，经过预混后灌入湿法研磨设备，研磨介质为氧化锆微球，研磨转速2000rpm，研磨期间物料温度控制在20℃以下，当物料中颗粒粒径D90=2μm时出料，然后在高速剪切机中进行黏土的阳离子交换反应，反应温度70℃，剪切速度30000rpm，反应时间24小时，得到浆料A。
(2)原位插层聚合:在浆料A中加入8333g对苯二甲酸(C8H6O4)，4027g乙二醇(C2H6O2)， 2.49g氧化锑(Sb2O3)，0.27g四水合乙酸钴(C4H14CoO8)，140μl磷酸三甲酯(C3H9O4P)，100g石墨烯粉末，预搅拌后进行湿法研磨，研磨介质为氧化锆微球，研磨转速2000rpm，研磨期间物料温度控制在20℃，当物料中颗粒粒径D90=2μm时出料并移入聚合反应釜，边搅拌边升温至120℃，抽真空脱水并用N2吹扫至不再收集到凝结水，升温至260℃开始缩聚脱水，在保证釜压安全的前提下释放水蒸气至不再收集到凝结水，升温至270℃，抽乙二醇至真空度低于90Pa以下，放料，得到聚酯复合吸附材料。
实施例3：
(1)黏土的阳离子交换:取黏土100g、四水甲酸铜(C2H2CuO4) 30g、醋酸锌(C4H10O6Zn) 28g和去离子水300ml配料，经过预混后灌入湿法研磨设备，研磨介质为氧化锆微球，研磨转速1900rpm，研磨期间物料温度控制在20℃以下，当物料中颗粒粒径D90=2μm时出料，然后在高速剪切机中进行黏土的阳离子交换反应，反应温度68℃，剪切速度25000rpm，反应时间30小时，得到浆料A。
(2)原位插层聚合:在浆料A中加入5554g对苯二甲酸(C8H6O4)，2684g乙二醇(C2H6O2)，1.66g氧化锑(Sb2O3)，0.18g四水合乙酸钴(C4H14CoO8)，93.4μl磷酸三甲酯(C3H9O4P)，80g石墨烯粉末，预搅拌后进行湿法研磨，研磨介质为氧化锆微球，研磨转速1900rpm，研磨期间物料温度控制在25℃，当物料中颗粒粒径D90=2μm时出料并移入聚合反应釜，边搅拌边升温至120℃，抽真空脱水并用N2吹扫至不再收集到凝结水，升温至260℃开始缩聚脱水，在保证釜压安全的前提下释放水蒸气至不再收集到凝结水，升温至280℃，抽乙二醇至真空度低于90Pa以下，放料，得到聚酯复合吸附材料。
Claims (3)
1.一种聚酯高分子/黏土复合吸附材料的制备方法，包括如下步骤：
(1)黏土的阳离子交换:取黏土100g、四水甲酸铜(C2H2CuO4) 21～35g、醋酸锌(C4H10O6Zn) 20～34g和去离子水200～400ml配料，经过预混后灌入湿法研磨设备，研磨介质为氧化锆微球，研磨转速1700～2000rpm，研磨期间物料温度控制在20℃以下，当物料中颗粒粒径D90=2μm时出料，然后在高速剪切机中进行黏土的阳离子交换反应，反应温度65~70℃，剪切速度20000~30000rpm，反应时间24～36小时，得到浆料A；
(2)原位插层聚合:在浆料A中加入2777～8333g对苯二甲酸(C8H6O4),1342～4027g乙二醇(C2H6O2)，0.83～2.49g氧化锑(Sb2O3)，0.09～0.27g四水合乙酸钴(C4H14CoO8)，46.7～140μ L 磷酸三甲酯(C3H9O4P)，50～100g石墨烯粉末，预搅拌后进行湿法研磨，研磨介质为氧化锆微球，研磨转速1700～2000rpm，研磨期间物料温度控制在20～30℃，当物料中颗粒粒径D90=2μm时出料并移入聚合反应釜，边搅拌边升温至120℃，抽真空脱水并用N2吹扫至不再收集到凝结水，升温至225～260℃开始缩聚脱水，在保证釜压安全的前提下释放水蒸气至不再收集到凝结水，升温至270～280℃，抽乙二醇至真空度低于90Pa以下，放料，得到聚酯高分子/黏土复合吸附材料；其中，
所用黏土为提纯过的蒙脱石(MMT)；
湿法研磨所用磨介氧化锆微球直径≤0.2mm。
2.一种根据权利要求1所述制备方法得到的聚酯高分子/黏土复合吸附材料。
3.一种根据权利要求2所述聚酯高分子/黏土复合吸附材料在污水有机物吸附的应用。
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398520A (zh) * | 2001-07-25 | 2003-02-26 | 广州擎天新材料研究开发有限公司 | 粘土复合抗菌剂及其制备方法 |
| CN101918324A (zh) * | 2007-10-31 | 2010-12-15 | 莫利康普矿物有限责任公司 | 用于处理被污染的流体的聚集体组合物 |
| CN101992132A (zh) * | 2010-11-25 | 2011-03-30 | 同济大学 | 离子交换型废水脱氮材料及其制备方法 |
| CN102002141A (zh) * | 2010-11-19 | 2011-04-06 | 安徽大学 | 聚氨酯-纳米高岭土复合材料的制备方法 |
| CN102658100A (zh) * | 2012-04-26 | 2012-09-12 | 江苏科技大学 | 聚丙烯酸-腐植酸-累托石复合吸附剂的制备方法 |
| CN103071451A (zh) * | 2011-10-25 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | 净化废水中重金属离子改性凹凸棒石粘土及制备方法 |
| CN103263896A (zh) * | 2013-05-30 | 2013-08-28 | 新疆大学 | 一种纤维素基聚合物/蒙脱土纳米复合吸附材料及其制备方法 |
| CN103709779A (zh) * | 2013-12-18 | 2014-04-09 | 天津一诺电子产品销售有限公司 | 一种聚合物基纳米复合材料的制备方法 |
| CN106334539A (zh) * | 2016-10-04 | 2017-01-18 | 青岛大学 | 一种阳离子聚合物改性蒙脱土吸附剂及其制备方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090286917A1 (en) * | 2007-12-20 | 2009-11-19 | Surbhi Mahajan | Improved catalyst system for polyester nanocomposites |
-
2017
- 2017-07-26 CN CN201710617802.0A patent/CN107456956B/zh active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1398520A (zh) * | 2001-07-25 | 2003-02-26 | 广州擎天新材料研究开发有限公司 | 粘土复合抗菌剂及其制备方法 |
| CN101918324A (zh) * | 2007-10-31 | 2010-12-15 | 莫利康普矿物有限责任公司 | 用于处理被污染的流体的聚集体组合物 |
| CN102002141A (zh) * | 2010-11-19 | 2011-04-06 | 安徽大学 | 聚氨酯-纳米高岭土复合材料的制备方法 |
| CN101992132A (zh) * | 2010-11-25 | 2011-03-30 | 同济大学 | 离子交换型废水脱氮材料及其制备方法 |
| CN103071451A (zh) * | 2011-10-25 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | 净化废水中重金属离子改性凹凸棒石粘土及制备方法 |
| CN102658100A (zh) * | 2012-04-26 | 2012-09-12 | 江苏科技大学 | 聚丙烯酸-腐植酸-累托石复合吸附剂的制备方法 |
| CN103263896A (zh) * | 2013-05-30 | 2013-08-28 | 新疆大学 | 一种纤维素基聚合物/蒙脱土纳米复合吸附材料及其制备方法 |
| CN103709779A (zh) * | 2013-12-18 | 2014-04-09 | 天津一诺电子产品销售有限公司 | 一种聚合物基纳米复合材料的制备方法 |
| CN106334539A (zh) * | 2016-10-04 | 2017-01-18 | 青岛大学 | 一种阳离子聚合物改性蒙脱土吸附剂及其制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| "聚对苯二甲酸乙二醇酯/蒙脱土纳米复合材料的制备、结构";徐锦龙;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20030615(第02期);B020-10 * |
| "载锌蒙脱石对大肠杆菌K88抗菌效果的影响";苗志国等;《吉林农业科学》;20070825;第32卷(第4期);第56-58页 * |
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