CN1212196C - 无机插层纳米催化剂及其制备方法 - Google Patents
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Abstract
本发明涉及一种无机插层纳米催化剂及其制备方法，该催化剂是以二元羧酸锌为插入物，以蒙脱土、云母、蛭石或高龄土等为基体的无机插层纳米催化剂。其制备方法是将无机基体粉末在600～1000℃下高温活化2～10小时，冷却后备用。将二元羧酸锌用强极性溶剂溶解后与无机基体进行插层反应30～120分钟，然后采用弱极性溶剂进行晶格修饰制得。本发明提供的催化剂具有制备工艺简单，催化效率高，选择性较好。
Description
技术领域
本发明涉及一种无机插层纳米催化剂及其制备方法，尤其是用于催化环氧化合物与二氧化碳的交替共聚反应，以合成高交替度的聚烷撑碳酸酯的无机插层纳米催化剂及其制备方法。
背景技术
环氧化合物与二氧化碳通过交替共聚反应可得到聚烷撑碳酸酯，可广泛用于低温隔氧薄膜、生物降解塑料、弹性体、胶粘剂、涂料等领域。合成该类聚合物可以有效地利用工业上大量废弃而对环境造成极大危害的温室气体——二氧化碳，同时产物具有生物降解性能，不会带来通常塑料所导致的白色污染，因而具有良好的经济和社会效益。这个反应的经典催化体系有以下几类：(一)、二乙基锌和等摩尔数的水，该体系的主催化剂二乙基锌对微量水汽和氧十分敏感，难以操作，尚须使用大量严格干燥的溶剂二氧六环，因而成本很高且效率低。(二)、采用卟啉金属络合物作催化剂，虽然催化效率有较大的提高，但此类络合物及其原料制备较繁琐，价格亦相当高，所制备的聚合物的玻璃化温度很低。(三)、采用二元羧酸锌盐作催化剂可以有比较满意的催化效率，并且生成的共聚产物交替度高，结构规整，产物性能优良。催化体系合成简单，聚合过程不需溶剂，催化剂成本也较低，但目前催化效率仍不够理想，戊二酸锌的催化效率在210克聚合物/克锌以下，而己二酸锌的催化活性则在65克聚合物/克锌以下。由以上几类经典催化剂出发合成共聚产物的催化成本仍难以被工业化生产所承受。
发明内容
本发明的目的是提供一种无机插层纳米催化剂及其制备方法，其制备方法工艺简单先进，成本较低，催化剂的效率高，选择性较好。
本发明无机插层纳米催化剂是以二元羧酸锌R(COO)2Zn为插入物，以具有无机片层结构无机矿物粉为无机基体的无机插层纳米催化剂，式中R为乙基、丙基、丁基、戊基、己基。无机基体可采用蒙脱土、云母、蛭石、或高龄土。
无机插层纳米催化剂的制备方法是先将无机基体微粉高温活化2～10小时，干燥冷却后备用；将二元羧酸锌用强极性溶剂溶解后对无机基体进行插层反应30～120分钟，然后采用弱极性溶剂在80～140℃下进行晶格修饰制得。使用的强极性溶剂为甲醇、乙二醇、二甲基甲酰胺、环丁砜、喹啉、N-环己基吡咯烷酮、乙二醇单丁醚或乙二醇单甲醚。采用的弱极性溶剂为苯、甲苯或二甲苯。
本发明提供的催化剂具有催化剂的效率高，选择性较好。本发明提供的催化剂在于燥的空气中稳定，有一定的吸湿性，但在一定条件下经加热即可脱水活化，不影响其催化活性。
二元羧酸锌的制备，现有技术可采用超声波振荡法和机械搅拌法。一种典型的超声波振荡法制备二元羧酸锌的方法是将二元羧酸与氧化锌按摩尔比100∶96～98放入反应器中，加入适量的反应介质如甲苯、二氯甲烷、苯等，超声振荡6～40小时，反应温度40～80℃，产率≥98％。机械搅拌法又分为一次加料法和滴加法，典型的一次加料法是将二元羧酸与氧化锌按摩尔比100∶96～98同时放入反应器中，放入适量的反应介质如甲苯、二氯甲烷、苯等，利用机械搅拌，反应4～20小时，反应温度50～100℃，产率≥95％；典型的滴加法是将氧化锌放入反应器中，加入适量的反应介质如甲苯、二氯甲烷、苯等，而将二元羧酸溶解于丙酮中，二者投料摩尔比与一次加料法相同，将二元羧酸的丙酮溶液按一定的速度滴加入剧烈搅拌的反应瓶中，反应温度60～100℃，滴加完毕后反应2～4小时，产率≥95％。以上各种方法最后均形成不溶于反应介质的白色沉淀；利用布氏漏斗抽滤而将这些白色沉淀收集，用丙酮洗涤除去未反应的二元羧酸，最后干燥即制得催化剂插入物——二元羧酸锌。
本发明制备方法工艺先进，其制备方法利用溶液插层和晶格修饰的方法将二元羧酸锌细化并分布在无机片层基体的表面和层间，增大了二元羧酸锌颗粒的比表面积，使能够成为活性中心的络合锌原子数大大增加。利用本发明无机插层纳米催化剂中催化效率最高的催化剂戊二酸锌插层纳米催化剂每生产1000克聚丙撑碳酸酯仅耗2.7克锌，高于已公开报导的本领域同类催化剂。
具体实施方式
实施例：一般操作
插入物二元羧酸锌制备：将二元羧酸和氧化锌按摩尔比100∶96～98放入反应瓶中，加入一定量的反应介质如甲苯、二氯甲烷、苯等，在40～80℃下超声振荡6～40小时或在50～100℃下机械搅拌4～20小时；也可将二元羧酸的丙酮溶液按一定速度滴加入加有氧化锌和一定量的反应介质的反应瓶中，温度60～100℃，滴加完毕后再反应2～4小时，全过程机械搅拌。将上述方法产生的白色沉淀过滤收集后用丙酮洗涤，干燥至恒重待用。
无机插层纳米催化剂制备：将无机基体微粉在600～1000℃下高温活化2～10小时，干燥冷却后备用。将二元羧酸锌用强极性溶剂甲醇、乙二醇、二甲基甲酰胺、环丁砜、喹啉、N-环己基吡咯烷酮、乙二醇单丁醚、乙二醇单甲醚等溶解后对无机基体插层反应30～120分钟，然后采用弱极性溶剂苯、甲苯、二甲苯等在80～140℃下进行晶格修饰制得。
环氧化合物与二氧化碳共聚：在500ml高压釜内加入一定量的催化剂(0.1～2.0g)于70℃下真空干燥24小时后降温至室温，然后加入环氧丙烷(PO)100～150ml，充入二氧化碳并加热，最终使釜内压力达到3.0～6.0MPa，釜内温度60～80℃，反应20～40小时后降温排出余气，开釜后取出产物聚丙撑碳酸酯的环氧丙烷本体溶液，加入一定量的三氯甲烷稀释，用甲醇沉淀，得粗产物，经干燥后得最终产物聚丙撑碳酸酯。
实施例1-5：
实施例1-5分别采用不同羧酸锌为插入物，以蛭石、蒙脱土、云母、高岭土等为无机基体的无机插层纳米催化剂，表1中列出了制备无机插层纳米催化剂的条件。表1列出的还有用所制得的无机插层纳米催化剂催化二氧化碳与环氧丙烷合成聚丙撑碳酸酯的条件和产率。实施例的结果表明用本发明的无机插层纳米催化剂：戊二酸锌、己二酸锌、庚二酸锌等的无机插层纳米催化剂可以得到极高的催化效率。
表1无机插层纳米催化剂的制备条件和催化结果
| 插入物 | 无机基体 | 基体用量(％) | 基体活化条件 | 晶格修饰条件 | 催化效率(克聚合物/克锌) | |
| 实施例1 | 丁二酸锌 | 蛭石 | 300 | 1000℃，4小时 | 苯，80℃ | 10.4 |
| 实施例2 | 戊二酸锌 | 蛭石 | 300 | 900℃，4小时 | 甲苯，110℃ | 410.8 |
| 实施例3 | 庚二酸锌 | 蒙脱土 | 300 | 800℃，2小时 | 对二甲苯，138℃ | 339.4 |
| 实施例4 | 己二酸锌 | 云母 | 300 | 750℃，2小时 | 甲苯，110℃ | 240.9 |
| 实施例5 | 辛二酸锌 | 高龄土 | 300 | 600℃，4小时 | 苯，80℃ | 128.8 |
注：1)聚合物(聚丙撑碳酸酯)的制备条件：60℃，48小时，二氧化碳压力5.2MPa；
2)无机基体用量以插入物为100％计。
Claims (4)
1、一种无机插层纳米催化剂，其特征是该催化剂是以二元羧酸锌R(COO)2Zn为插入物，以具有无机片层结构无机矿物粉为无机基体的无机插层纳米催化剂，式中R为乙基、丙基、丁基、戊基或己基。
2、根据权利要求1中所述的催化剂，其特征在于具有无机片层结构无机矿物粉为蒙脱土、云母、蛭石或高龄土。
3、一种如权利要求1或2所述的无机插层纳米催化剂的制备方法，其特征是先将无机基体微粉在600～1000℃下高温活化2～10小时，干燥冷却后备用；将二元羧酸锌用强极性溶剂溶解后对无机基体插层反应30～120分钟，然后采用弱极性溶剂在80～140℃进行晶格修饰制得。
4、根据权利要求3所述的无机插层纳米催化剂的制备方法，其特征在于强极性溶剂为甲醇、乙二醇、二甲基甲酰胺、环丁砜、喹啉、N-环己基吡咯烷酮、乙二醇单丁醚或乙二醇单甲醚，弱极性溶剂为苯、甲苯或二甲苯。
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| US10/803,310 US20040214718A1 (en) | 2003-04-25 | 2004-03-18 | Inorganic intercalating nano-catalyst for the fixation of carbon dioxide into aliphatic polycarbonate and a process for preparing the same |
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| CN101468320B (zh) * | 2007-12-28 | 2010-12-15 | 聊城大学 | 无机物插层纳米羧酸锌催化剂及其制备方法 |
| US20140005415A1 (en) * | 2010-12-07 | 2014-01-02 | Texas State University-San Marcos | Immobilization of ionic liquids via mechnochemical intercalation in layered materials |
| CN102863824B (zh) * | 2012-08-25 | 2014-04-02 | 华南理工大学 | 一种不饱和羧酸锌盐功能化石墨烯的制备方法 |
| KR101640244B1 (ko) | 2013-10-30 | 2016-07-15 | 주식회사 엘지화학 | 유기 아연 촉매의 제조 방법 및 폴리알킬렌 카보네이트 수지의 제조 방법 |
| KR101639364B1 (ko) | 2013-11-04 | 2016-07-13 | 주식회사 엘지화학 | 유기 아연 촉매 |
| EP3048129B1 (en) | 2013-11-18 | 2020-07-29 | LG Chem, Ltd. | Organic zinc catalyst, preparation method therefor, and method for preparing polyalkylene carbonate resin by using same |
| EP3048128B1 (en) | 2013-11-18 | 2018-04-25 | LG Chem, Ltd. | Method for preparing polyalkylene carbonate resin |
| CN106800298A (zh) * | 2016-12-29 | 2017-06-06 | 高州市兆翔新材料有限公司 | 一种改性高岭土 |
| CN107459046B (zh) * | 2017-06-29 | 2020-01-14 | 枣庄市三兴高新材料有限公司 | 一种甲醇/高岭石层间接枝复合物及其快速制备方法 |
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| US3585168A (en) * | 1968-09-21 | 1971-06-15 | Shohei Inoue | Process for producing copolymer of epoxide and carbon dioxide |
| US3953383A (en) * | 1972-07-21 | 1976-04-27 | Nippon Oil Seal Industry Co., Ltd. | Catalytic process for copolymerizing epoxy compounds with carbon dioxide |
| US3900424A (en) * | 1972-07-21 | 1975-08-19 | Nippon Oil Seal Ind Co Ltd | Catalyst for copolymerizing epoxy compounds with carbon dioxide |
| US4268684A (en) * | 1980-02-25 | 1981-05-19 | The Dow Chemical Company | Preparation of carbamates from aromatic amines and organic carbonates |
| US4510257A (en) * | 1983-12-08 | 1985-04-09 | Shell Oil Company | Silica-clay complexes |
| US4783445A (en) * | 1987-12-14 | 1988-11-08 | Arco Chemical Company | Soluble epoxide/carbon dioxide copolymerization catalysts |
| EP0358326B1 (en) * | 1988-08-09 | 1996-12-27 | Mitsui Petrochemical Industries, Ltd. | Process for preparing a zinc-containing solid catalyst and process for preparing polyalkylene carbonate |
| US5026676A (en) * | 1989-06-07 | 1991-06-25 | Air Products And Chemicals, Inc. | Catalyst for the copolymerization of epoxides with CO2 |
| US7354880B2 (en) * | 1998-07-10 | 2008-04-08 | Univation Technologies, Llc | Catalyst composition and methods for its preparation and use in a polymerization process |
| US6482903B1 (en) * | 1999-12-15 | 2002-11-19 | Univation Technologies, Llc | Method for preparing a supported catalyst system and its use in a polymerization process |
| US6593267B2 (en) * | 2000-12-18 | 2003-07-15 | Univation Technologies, Llc | Method for preparing a supported catalyst system and its use in a polymerization process |
| CN1120048C (zh) * | 2001-12-18 | 2003-09-03 | 中国科学院广州化学研究所 | 负载型二元羧酸锌催化剂及其制备方法 |
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