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锌-钴氰化络合物催化剂的改性及其在聚醚碳酸酯二元醇合成中的应用

吴冬凡 张源萍 李其峰 亢茂青 王军威

吴冬凡, 张源萍, 李其峰, 亢茂青, 王军威. 锌-钴氰化络合物催化剂的改性及其在聚醚碳酸酯二元醇合成中的应用[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022016
引用本文: 吴冬凡, 张源萍, 李其峰, 亢茂青, 王军威. 锌-钴氰化络合物催化剂的改性及其在聚醚碳酸酯二元醇合成中的应用[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022016
WU Dong-fan, ZHANG Yuan-ping, LI Qi-feng, KANG Mao-qing, WANG Jun-wei. Modification of Zn-Co DMC catalyst and its application in the synthesis of poly(ether-carbonate) polyols[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022016
Citation: WU Dong-fan, ZHANG Yuan-ping, LI Qi-feng, KANG Mao-qing, WANG Jun-wei. Modification of Zn-Co DMC catalyst and its application in the synthesis of poly(ether-carbonate) polyols[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022016

锌-钴氰化络合物催化剂的改性及其在聚醚碳酸酯二元醇合成中的应用

doi: 10.19906/j.cnki.JFCT.2022016
基金项目: 山西省重点研发计划 (201903D121104)资助
详细信息
    通讯作者:

    Tel:13934558196, E-mail:liqf@sxicc.ac.cn

  • 中图分类号: O633.4

Modification of Zn-Co DMC catalyst and its application in the synthesis of poly(ether-carbonate) polyols

Funds: The project was supported by Key Research and Development Program of Shanxi Province (201903D121104)
  • 摘要: 双金属氰化物(double mental cyanide,DMC)是一种用于二氧化碳与环氧丙烷(PO)共聚反应的催化剂。DMC催化剂是具有晶体结构的有机金属配合物,其催化活性与结晶度密切相关。加入配体、共配体能够破坏立方晶体结构、增加无定形态结构从而降低结晶度。研究证明,以叔丁醇为配体的DMC催化剂活性较高,但是对共配体的使用则鲜有报道。本研究使用不同共配体(Span80、Tween80、D400、D2000)对DMC催化剂改性以达到两个目的:一是,降低结晶度,提高催化剂活性;二是,减小催化剂粒径。此外,利用PO与CO2的共聚反应对催化剂性能进行考察。结果表明,使用D2000作为共配体改性后的DMC+D2000催化剂,催化活性为1547 g/gcat,聚合产物中碳酸酯单元占聚合部分的质量分数为25.3%,选择性为92.1%。
  • 图  1  DMC催化剂反应机理[12]

    Figure  1  Reaction mechanism of DMC catalyst[12]

    图  2  共配体存在下DMC催化剂形成过程

    Figure  2  DMC catalyst formation process in the presence of co-complexing agent

    图  3  不同共配体改性的DMC催化剂的FT-IR谱图

    Figure  3  FT-IR spectra of DMC catalysts modified by different co-complexing agents

    a: DMC; b: DMC+S80; c: DMC+T80; d: DMC+D2000; e: DMC+D400

    图  4  不同共配体改性催化剂的XRD谱图

    Figure  4  XRD patterns of catalysts modified by different co-complexing agents

    a: DMC; b: DMC+S80; c: DMC+T80; d: DMC+D2000; e: DMC+D400

    图  5  不同共配体改性的催化剂粒径分布

    Figure  5  Mean volume diameter distribution of catalysts modified by different co-complexing agents

    ▼: DMC+S80; ■: DMC+T80; ▲: DMC+D2000; ●: DMC+D400; ◆: DMC

    图  6  不同共配体改性的催化剂SEM照片

    Figure  6  SEM images of catalysts modified by different co-complexing agents

    图  7  不同共配体改性的催化剂TG和DTG曲线

    Figure  7  TG and DTG curves of DMC catalysts modified by different co-complexing agents

    图  8  聚醚碳酸酯二元醇的1H NMR(a)和GPC(b)谱图

    Figure  8  1H NMR spectra (a) and GPC spectra (b) of poly(ether-carbonate) polyols

    a: DMC; b: DMC+S80; c: DMC+T80; d: DMC+D2000; e: DMC+D400

    表  1  共配体的种类及结构

    Table  1  Types and structures of co-complexing agents

    TypesMnFunctional groupSolubilityStructure
    Span80428–OH+
    Tween801365–OH+++
    D400400–NH2++
    D20002000–NH2
    Solubility:Degree of dissolution of the sample in water,(+):soluble;(–):insouble
    下载: 导出CSV

    表  2  不同条件下CO2与 PO共聚反应

    Table  2  Copolymerization of PO and CO2 catalyzed under different conditions

    EntryCTA/PO (mass ratio)Reaction period/ht/℃p/MPaa Mn/(g·mol−1)b​​​​CU'$
    /mol%
    c Selectivity
    s/%
    10.2520802105819.094.7
    20.2512802120423.891.8
    30.1612802210921.292.2
    40.251270279114.195.4
    50.2512902182025.282.7
    60.25121002191515.182.9
    7 [18]04800.567000-
    8 [25]0.04810803.8605032.05
    The Zn-Co double mental cyanide catalyst was used in copolymerization; Entry1 is one-step method, entry 2–6 is continuous method;
    a:Mn=56.1*1000f /Qv; $
    b: the molar fraction of carbonate linkages in the produced polymer; [Carbonate]/([carbonate] + [ether]) ratio determined by 1H NMR spectra;
    c: the weight percentage of poly(ether-carbonate) polyols in the total crude product
    下载: 导出CSV

    表  3  不同催化剂作用的CO2与 PO共聚反应a

    Table  3  Copolymerization of PO and CO2 catalyzed by different catalysts a

    EntryCatalystb Mn
    /(g·mol−1)
    c${f}_{ {\rm{CO} }_2}^{\prime }$
    /mol/%
    dCU'$
    /mol/%
    e Selectivity
    s/%
    f PDIg Yield
    /(g·${\rm{g}}^{-1}_{\rm{cat}} $)
    1DMC120419.223.891.81.241235
    2DMC+S8060332.942.987.41.22646
    3DMC+T80114816.619.895.01.271079
    4DMC+D2000167920.125.392.11.301547
    5DMC+D40080334.853.389.41.50934
    a: Reaction conditions: W(catalyst)=40 mg, CTA/PO (mass ratio)=0.25; stage of activation: t1=120 ℃; the stage of adding ingredients: t2=80 ℃, p2=2.0 MPa, t2=10 h;
    $
    b:Mn=56.1*1000f /Qv; c: the molar fraction of carbon dioxide insertion in the produced polymer;
    d: the molar fraction of carbonate linkages in the produced polymer;
    e: the weight percentage of poly(ether-carbonate) polyols in the total crude product;
    f: Polydispersity index determined by gel permeation chromatograph;
    g: Yield/% = mPO/ mcat
    下载: 导出CSV

    表  4  不同催化剂催化CO2与 PO共聚反应对比

    Table  4  Comparison of different catalysts for the copolymerization of PO and CO2

    No. co-complexing
    agent
    CTA/PO/DMC
    (g/g/mg)
    CTAt(℃)/
    p(MPa)
    a Mn/
    (g·mol−1)
    bCU'$/
    mol%
    c Selectivity
    s/%
    dPDI
    1[17]47/76/100PPG40080/210202594.91.06
    2[25]2.5/25.6/10H2O80/5152005879.52.3
    3[28]13/83/10BPA95/4200031872.88
    4[29]PEG100030/90/41PPG725105/226609.499.65.97
    5D200030/120/60PPG40080/216792592.11.3
    a: Mn=56.1*1000f/ Qv$;
    b: the molar fraction of carbon dioxide insertion in the produced polymer;
    c: the molar fraction of carbonate linkages in the produced polymer;
    d: the weight percentage of poly(ether-carbonate) polyols in the total crude product
    下载: 导出CSV
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  • 收稿日期:  2021-12-27
  • 录用日期:  2022-03-04
  • 修回日期:  2022-02-21
  • 网络出版日期:  2022-03-16

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