CN1120048C - 负载型二元羧酸锌催化剂及其制备方法 - Google Patents
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- XKEVNNZBABNSFU-UHFFFAOYSA-N heptanedioic acid zinc Chemical compound [Zn].C(CCCCCC(=O)O)(=O)O XKEVNNZBABNSFU-UHFFFAOYSA-N 0.000 description 2
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- HCHKCACWOHOZIP-IGMARMGPSA-N Zinc-65 Chemical compound [65Zn] HCHKCACWOHOZIP-IGMARMGPSA-N 0.000 description 1
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Abstract
本发明涉及一种负载型二元羧酸锌催化剂及其制备方法，该催化剂是以二元羧酸锌为主体，以二氧化硅为载体的负载型催化剂，其中二元羧酸锌与二氧化硅的重量比为1∶1～15。其制备方法是将二氧化硅粉末在600～800℃下高温活化10～16小时，干燥冷却后，将二元羧酸锌与二氧化硅按所述重量比混合，高速粉碎研磨30～120分钟制得。本发明提供的催化剂具有催化效率高和提高产物分子量的特点，且制法简单。
Description
本发明涉及一种负载型二元羧酸锌催化剂及其制备方法，尤其是用于催化环氧化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负载型二元羧酸锌载体催化剂及其制备方法。
环氧化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(详见Inoue，S；Koinuna，H；Tsuruta，T；Makromko，Chem.1969，130，210)。但该体系的主催化剂二乙基锌对水汽和氧十分敏感，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(参见Inoue，S；Aida，T；ACS Symp，Ser；1985，286，137)但此类络合物及其原料制备较繁琐，价格亦相当高。(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(参见M.Ree；J.Y.Bae；J.H.Jung；T.J.Shin，Journal of Polymer Sci.，Part A：Polymer Chemistry，1999，37，1863)，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生产所承受。
本发明的目的是提供一种高效、稳定、安全且具有较好重复性的催化体系，将此催化体系用于坏氧化物与二氧化碳的共聚，可获得与现有催化体系相比较而言的极高的催化效率和低得多的催化成本，从而为聚烷撑碳酸酯真正实现工业化生产提供高效催化体系保证。
本发明的另一个目的是提供该催化剂简单易行的制备方法。
本发明提供的负载型二元羧酸锌催化剂是以二元羧酸锌R(COO)2Zn为主体，以二氧化硅为载体的负载型催化剂，其中二元羧酸锌与二氧化硅的重量比为1∶1～15。
式中R为乙基、丙基、丁基、戊基、己基。
其中优选以己二酸锌为主体，以二氧化硅为载体的负载型催化剂。
二元羧酸锌与二氧化硅的重量比以1∶2～5为佳。
本发明的催化剂为白色粉末，不溶于水和有机溶剂，在干燥的空气中稳定，有一定的吸湿性，但经加热即可脱水活化，不影响其催化活性。
本发明提供的催化剂的制备方法是将二氧化硅粉末在600～800℃下高温活化10～16小时，干燥冷却后，将二元羧酸锌与二氧化硅按所述重量比混合，高速粉碎研磨30～120分钟，即制得二氧化硅负载的二元羧酸锌催化剂。
其中载体SiO2可以为气相法二氧化硅(白炭黑)、柱层析用硅胶，以及试剂级二氧化硅粉末等。对气相法二氧化硅，粒径优选200～300纳米左右，
在将二元羧酸锌负载在载体二氧化硅上时，粉碎研磨可采用行星式球磨机，研磨转速200～500转/分钟。
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主体——二元羧酸锌。
本发明的催化剂利用机械研磨的方法将二元羧酸锌颗粒粉碎细化并分布在坚硬的二氧化硅粒子上，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。另外二氧化硅具有一定的吸水能力，利用其可以吸附原料二氧化碳和环氧化物中的微量水份，从而也可以进一步提高催化效率和产物的分子量。
利用本发明系列催化剂中催化效率最高的催化剂负载戊二酸锌每生产1公斤聚丙撑碳酸酯仅耗2.8克锌，利用负载己二酸锌每生产1公斤聚丙撑碳酸酯也只需耗4.3克锌，利用负载庚二酸锌每生产1公斤聚丙撑碳酸酯也只耗3.1克锌，均远远高于已公开报导的本领域同类催化剂，并且制备己二酸锌的原料己二酸为大宗工业产品，价格仅为戊二酸的1/9，因而具有很低的催化成本和很强的竞争优势。
实施例：
一般操作
主催化剂制备：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。
载体催化剂制备：将二氧化硅如气相法SiO2，柱层析用硅胶，以及试剂级粉末状二氧化硅粉末于马弗炉内700℃下高温活化12小时。将二元羧酸锌与适量二氧化硅(重量比为1∶1～1∶20))放入真空球磨罐中，在行星式球磨机中以每分200转至500转的转速粉碎研磨30～60分钟，即制得载体催化剂。
环氧化物与二氧化碳共聚：在500ml高压釜内加入一定量的催化剂(0.1～1.0g)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，经酸洗脱去催化剂，水洗至中性等步骤，最后用甲醇沉淀，得粗产物，经干燥后得最终产物聚丙撑碳酸酯。
实施例1-8：
实施例1-8是催化剂主体二元羧酸锌的制备条件和结果，从表1列出的结果可以看出在不同条件下采用不同二元羧酸与氧化锌反应，均可以得到满意的产率。
实施例9-13：
实施例9-13分别采用实施例1，2，6，7，8制得的主催化剂与二氧化硅负载，表中列出了制备载体催化剂的条件。表2中列出的还有用所制得的载体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载体催化剂：负载戊二酸锌、负载己二酸锌、负载庚二酸锌可以得到极高的催化效率，在对比例中催化剂戊二酸锌未经过负载，达到的产率就只有实施例10的53.3％。
表1 催化剂主体二元羧酸锌的制备条件和结果
| 二元羧酸 | 二元羧酸/氧化锌 | 反应温度(℃) | 反应时间(小时) | 反应类型 | 产率(％) | |
| 实施例1 | 丁二酸 | 0.98 | 60 | 10 | 机械搅拌a | 95.4 |
| 实施例2 | 戊二酸 | 0.98 | 55 | 10 | 机械搅拌a | 99.78 |
| 实施例3 | 戊二酸 | 0.98 | 60 | 20 | 超声波振荡 | 99.48 |
| 实施例4 | 戊二酸 | 0.98 | 90 | 8 | 机械搅拌b | 97.66 |
| 实施例5 | 己二酸 | 0.96 | 80 | 10 | 机械搅拌a | 99.42 |
| 实施例6 | 己二酸 | 0.96 | 80 | 20 | 超声波振荡 | 98.94 |
| 实施例7 | 庚二酸 | 0.98 | 60 | 10 | 机械搅拌b | 99.22 |
| 实施例8 | 辛二酸 | 0.96 | 80 | 12 | 机械搅拌a | 95.20 |
注：机械搅拌a表示一次加料法；机械搅拌b表示滴加法。
表2 载体催化剂的制备条件和催化结果
| 催化剂主体 | 二氧化硅类型 | 载体用量(％) | 载体活化条件 | 负载条件 | 催化效率(克聚合物/克锌) | |
| 实施例9 | 丁二酸锌 | 气相法二氧化硅 | 200 | 700℃，12小时 | 350转/分，30分 | 9.38 |
| 实施例10 | 戊二酸锌 | 气相法二氧化硅 | 200 | 600℃，14小时 | 350转/分，30分 | 358.8 |
| 实施例11 | 己二酸锌 | 气相法二氧化硅 | 200 | 800℃，16小时 | 350转/分，30分 | 234.9 |
| 实施例12 | 庚二酸锌 | 试剂级二氧化硅 | 300 | 750℃，12小时 | 250转/分，60分 | 325.4 |
| 实施例13 | 辛二酸锌 | 试剂级二氧化硅 | 300 | 700℃，10小时 | 250转/分，60分 | 116.8 |
| 对比例 | 戊二酸锌 | --------- | ---- | ------- | 191.4 |
注：1)聚合物(聚丙撑碳酸酯)的制备条件：60℃，40小时，二氧化碳压力5.2MPa；
2)载体用量以催化剂主体为100％计；
3)对比例参见M.Ree；J.Y.Bae；，J.H.Jung；T.J.Shin，Journal of Polymer
Sci.，Part A：Polymer Chemistry，1999，37，1863
Claims (7)
1、一种负载型二元羧酸锌催化剂，其以二元羧酸锌R(COO)2Zn为主体，以二氧化硅为载体的负载型催化剂，其中二元羧酸锌与二氧化硅的重量比为1∶1～15，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，其特征在于所述二元羧酸锌为己二酸锌。
3、根据权利要求1或2中所述的催化剂，其特征在于二元羧酸锌与二氧化硅的重量比为1∶2～5。
4、一种制备权利要求1～3中所述催化剂的方法，先将二氧化硅粉末在600～800℃下高温活化10～16小时，干燥冷却后，将二元羧酸锌与二氧化硅按所述重量比混合，高速粉碎研磨30～120分钟，即制得二氧化硅负载的二元羧酸锌催化剂。
5、根据权利要求4中所述的方法，其特征在于所述载体SiO2选自气相法二氧化硅、柱层析用硅胶，以及试剂级二氧化硅粉末。
6、根据权利要求5中所述的方法，其特征在于所述气相法二氧化硅粒径为200～300纳米。
7、根据权利要求4或5中所述的方法，其特征在于所述粉碎研磨采用行星式球磨机，研磨转速200～500转/分钟。
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| CN1212196C (zh) * | 2003-04-25 | 2005-07-27 | 中山大学 | 无机插层纳米催化剂及其制备方法 |
| CN100410294C (zh) * | 2006-04-18 | 2008-08-13 | 中国科学院广州化学研究所 | 一种聚甲基乙撑-乙撑碳酸酯及其制备方法 |
| CN101759849B (zh) * | 2009-09-18 | 2012-09-26 | 广州科梦催化材料有限公司 | 用于二氧化碳和环氧丙烷共聚合的锌羟基酸类络合物催化剂及制备方法 |
| TR201202779A2 (tr) | 2012-03-12 | 2013-10-21 | Petkim Petrokimya Holding Anonim Sirketi | Polietilen karbonat üretim yöntemi. |
| EP2664641B1 (en) | 2012-05-18 | 2018-04-25 | Petkim Petrokimya Holding Anonim Sirekti | Method for producing polyethylene carbonate with metal salts |
| CN102766039B (zh) * | 2012-07-27 | 2015-05-13 | 湛江师范学院 | 一种二元羧酸锌催化剂的制备方法 |
| CN102872912B (zh) * | 2012-09-18 | 2014-04-23 | 哈尔滨理工大学 | 用于合成苯氨基甲酸甲酯的催化剂及其制备和应用方法 |
| JP6078166B2 (ja) | 2013-05-27 | 2017-02-08 | エルジー・ケム・リミテッド | ポリアルキレンカーボネートの製造方法 |
| 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 |
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| US10047196B2 (en) | 2013-11-18 | 2018-08-14 | Lg Chem, Ltd. | Organic zinc catalyst, and manufacturing method thereof and manufacturing method of polyalkylene carbonate resin using the same (as amended) |
| EP3310845B1 (en) | 2015-06-15 | 2022-02-23 | King Abdullah University Of Science And Technology | Use of additives to fine-tune the composition of carbonate units in the polymer formed by copolymerization of co2 with epoxide: application to the synthesis of polycarbonate-based block copolymers and of telechelics |
| EP3219741A1 (de) * | 2016-03-18 | 2017-09-20 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
| KR102000129B1 (ko) * | 2016-03-24 | 2019-07-15 | 주식회사 엘지화학 | 유기 아연 담지 촉매, 이의 제조 방법, 및 상기 촉매를 이용한 폴리알킬렌 카보네이트 수지의 제조 방법 |
| EP3794055A1 (en) | 2018-05-17 | 2021-03-24 | King Abdullah University of Science and Technology | <sup2/>? <sub2/>?2?supported onium salts as initiators for the synthesis of polycarbonates by copolymerization of cowith epoxides |
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| US4824969A (en) * | 1984-12-24 | 1989-04-25 | Exxon Research & Engineering Co. | Process for preparing cyclic carbonate esters from olefins in a single reaction mixture |
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