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α-二亚胺镍(Ⅱ)催化乙烯与乙烯基三甲氧基硅烷共聚

张丹枫 张文杰 牛犇 仝鑫

张丹枫, 张文杰, 牛犇, 仝鑫. α-二亚胺镍(Ⅱ)催化乙烯与乙烯基三甲氧基硅烷共聚[J]. 华东理工大学学报(自然科学版). doi: 10.14135/j.cnki.1006-3080.20220531001
引用本文: 张丹枫, 张文杰, 牛犇, 仝鑫. α-二亚胺镍(Ⅱ)催化乙烯与乙烯基三甲氧基硅烷共聚[J]. 华东理工大学学报(自然科学版). doi: 10.14135/j.cnki.1006-3080.20220531001
ZHANG Danfeng, ZHANG Wenjie, NIU Ben, TONG Xin. Copolymerization of Ethylene and Vinyl Trimethoxysilane with α-diimine Nickel (II) Catalysts[J]. Journal of East China University of Science and Technology. doi: 10.14135/j.cnki.1006-3080.20220531001
Citation: ZHANG Danfeng, ZHANG Wenjie, NIU Ben, TONG Xin. Copolymerization of Ethylene and Vinyl Trimethoxysilane with α-diimine Nickel (II) Catalysts[J]. Journal of East China University of Science and Technology. doi: 10.14135/j.cnki.1006-3080.20220531001

α-二亚胺镍(Ⅱ)催化乙烯与乙烯基三甲氧基硅烷共聚

doi: 10.14135/j.cnki.1006-3080.20220531001
基金项目: 上海市重点学科和重点实验室项目(08DZ2230500)
详细信息
    作者简介:

    张丹枫(1965—),女,江苏宜兴人,副教授,博士,从事烯烃配位聚合研究。zdf93102@ecust.edu.cn

  • 中图分类号: O631;O614.81

Copolymerization of Ethylene and Vinyl Trimethoxysilane with α-diimine Nickel (II) Catalysts

  • 摘要: 采用一系列不同结构的α-二亚胺镍(Ⅱ)催化剂,在倍半乙基氯化铝(EASC)作用下,催化乙烯和乙烯基三甲氧基硅烷(VTMoS)共聚。研究了催化剂结构、VTMoS浓度、催化剂用量、Al/Ni摩尔比、乙烯压力、聚合时间和溶剂等对共聚的影响,得到了最优化的催化工艺条件。采用高温核磁(NMR)、傅利叶红外光谱(FTIR)和差示扫描量热分析(DSC)表征了共聚物的微观结构和熔点,等离子体发射光谱测定了共聚物中的硅含量,平衡溶胀法分析了共聚物的交联程度以及共聚物交联网络的均匀性。研究结果表明,以 C4 为催化剂,乙烯压力为2~3 MPa,催化活性高达106 g/(molNi·h),共聚物中硅含量在0.8%~2.1%。

     

  • 1.  α-diimine nickel(II) complexes (C1-C5)

    图  1  乙烯/VTMoS共聚物的1H NMR谱图(表2中Entry 4)

    Figure  1.  1H NMR of ethylene/VTMoS copolymer (entry 4 in Table 2)

    图  2  乙烯/VTMoS共聚物的13C NMR谱图(表2中Entry 4)

    Figure  2.  13C-NMR of ethylene/VTMoS copolymer (entry 4 in Table 2)

    图  3  乙烯/VTMoS共聚物的红外谱图(表2中Entry 5)

    Figure  3.  FTIR spectrum of ethylene/VTMoS copolymer (entry 5 in Table 2)

    图  4  乙烯/VTMoS共聚物的DSC图(表2中Entry 3~5)

    Figure  4.  DSC curve of ethylene/VTMoS copolymers (entry 3~5 in Table 2)

    表  1  反应条件对催化剂C4催化乙烯/VTMoS共聚合的影响

    Table  1.   Influence of reaction parameters on copolymerization of ethylene/VTMoS by catalyst C4

    Entry[Si]/
    (mol/L)
    [Cat]/
    μmol
    nAl/nNiPC2H2
    /MPa
    t/
    h
    Activity/
    (105g/mol Ni·h)
    f a% gel aMc a
    g/mol
    105400117.89---
    20.505400116.5311.3996.952902.25
    31.005400113.2410.2665.482382.63
    41.505400110.02---
    50.502.5400112.129.4998.682048.10
    60.5010400113.267.0196.341126.44
    70.505200114.336.9098.921092.69
    80.505800116.5110.1589.932332.06
    90.5051000119.016.4889.47961.30
    100.5054000.511.195.1395.91589.23
    110.5054002110.4112.3791.463394.02
    120.5054003110.0022.1890.069858.99
    130.50540010.57.506.9097.331093.48
    140.505400123.187.1480.921169.58
    150.505400142.048.3481.751593.30
    160.50540011trance---
    170.5054001111.6323.3884.6610829.44
    Co-catalyst: AlEt2Cl; Entries 1-15, solvent: toluene, entry 16, solvent: hexane; entry 17, solvent: dichloromethane. Temperature: 25°C; V (toluene)=50 mL; a. f, % gel and Mc were determined by solvent swelling and extraction of the sample under refluxing p-xylene (139 °C).
    下载: 导出CSV

    表  2  催化剂结构对乙烯/VTMoS共聚的影响

    Table  2.   Influence of catalyst structures on ethylene/VTMoS copolymerization

    EntryCatalyst
    structure
    Activity/
    (105g·mol−1Ni·h−1)
    f agel a/%Mc a/(g·mol−1)Sib/%
    1C10.14----
    2C20.7213.8570.764188.201.7
    3C30.706.9047.971091.621.2
    4C46.5311.3996.952902.252.1
    5C50.849.9473.422240.580.82
    Catalyst dosage: 5 μmol; [VTMoS] = 0.50 mol/L; nAl/nNi = 400, Ethylene pressure: 1 MPa; Temperature: 25 °C; Time: 1 h; V (total) = 50 mL; Solvent: toluene; a. f, % gel and Mc were determined by solvent swelling and extraction of the sample under refluxing p-xylene (139 °C). b. Si % was determined by inductively coupled plasma (ICP).
    下载: 导出CSV
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  • 收稿日期:  2022-05-31
  • 网络出版日期:  2022-09-14

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