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冠醚络合高活性双金属氰化物制备及CO2与环氧丙烷共聚
  • ISSN号:0253-9837
  • 期刊名称:《催化学报》
  • 时间:0
  • 分类:O[理学]
  • 作者机构:[1]佛山科学技术学院食品与园艺学院,广东佛山528231, [2]中国科学院广州化学研究所,广东广州510650, [3]中国科学院大学,北京100049
  • 相关基金:国家自然科学基金(20274053);广东省自然科学基金(9151065004000005);佛山市科技计划(2014GA000425,2014AG10007).
中文摘要:

首次在共沉淀过程中添加18-冠-6醚络合生成的钾离子得到了均一的高活性冠醚络合的锌-钴双金属催化剂,并用红外光谱(FTIR)、扫描电镜(SEM)、热重红外(TGA-IR)和X射线衍射(XRD)进行了表征.元素分析发现K含量为1.2%.FTIR表明未加冠醚络合的双金属催化剂离心后上下部分呈现不同的络合状态,而冠醚络合的双金属催化剂仍保持均一.SEM表明冠醚络合的双金属催化剂为均一松散的结构.由于生成的钾离子被冠醚络合,不影响聚合反应效果.TGA-IR表明冠醚不仅络合K离子,还参与对金属活性中心的络合.XRD表明此催化剂具有低的结晶度.所制冠醚络合的锌-钴双金属催化剂能成功催化CO2与环氧丙烷共聚,其中CDMC3催化得到的共聚物碳酸酯含量为47.8%,副产物环状碳酸酯为1.5%,催化效率高达5122 g/g催化剂(32600 g/g Zn),明显优于不添加冠醚以同样工艺制备的DMC1(共聚物碳酸酯含量29.2%,副产物环状碳酸酯3.3%,催化效率4100 g/g催化剂(16300g/g Zn).与不添加冠醚8次洗涤离心得到的DMC2相当(共聚物碳酸酯含量48.3%,副产物环状碳酸酯含量2.4%,催化效率5073 g/g催化剂(16400 g/g Zn)).基于此结果提出了两步的反应机理假设.

英文摘要:

Double metal cyanide (DMC) catalysts are generally prepared by coprecipitation of potassium hex-acyanocobaltate(III) with zinc chloride followed by complexation with tert-butanol, and these ma-terials have been used for several decades in the copolymerization of CO2 and epoxides. However, the catalytic efficiency of DMC catalysts can be adversely affected by the presence of excess K+, and the preparation of these catalysts can therefore become complicated and time-consuming because of the multiple washing and centrifugation stages required for the removal of the excess K+. In this study, 18-crown-6 ether was used as an effective co-complexing agent for the removal of K+. A series of DMCs containing 18-crown-6 were prepared with different quantities of the crown ether and different washing times. The resulting crown ether-complexing catalysts (CDMCs) and DMC cata-lysts without crown ether were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis-IR and X-ray diffraction. These characterization results showed that the inclusion of 18-crown-6 allowed for the formation of uniform and highly dispersed CDMC catalysts. In contrast, the DMC catalysts prepared in the absence of 18-crown-6 became uneven and delaminated during the purification by centrifugation, with high- and low-density portions of the material forming on the bottom and top of the catalyst cakes, respec-tively. The inclusion of 18-crown-6 not only trapped K+ but also participated in the complexion process. The complexion of tert-BuOH and 18-crown-6 led to a less crystalline form of the CDMC catalyst. Elemental analysis revealed that CDMC1 contained 1.2%K+. The copolymer was obtained by the copolymerization of CO2 with propylene oxide using CDMC3 catalyst, which was superior to the copolymer prepared using DMC1. CDMC3 was as active as DMC2 prepared without the crown ether but with seven washing steps. A hypothetical two-stage catalytic mechanism was proposed.

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期刊信息
  • 《催化学报》
  • 北大核心期刊(2011版)
  • 主管单位:中国科学院
  • 主办单位:中国化学会 中国科学院大连化学物理研究所
  • 主编:李灿 张涛
  • 地址:大连市沙河口区中山路457号
  • 邮编:116023
  • 邮箱:chxb@dicp.ac.cn
  • 电话:0411-84379240
  • 国际标准刊号:ISSN:0253-9837
  • 国内统一刊号:ISSN:21-1195/O6
  • 邮发代号:8-93
  • 获奖情况:
  • 第三届国家期刊奖提名奖,中国科协精品科技期刊示范项目
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),荷兰文摘与引文数据库,美国工程索引,美国剑桥科学文摘,美国科学引文索引(扩展库),日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),英国英国皇家化学学会文摘,中国北大核心期刊(2000版)
  • 被引量:19199