高等学校化学学报 ›› 2012, Vol. 33 ›› Issue (12): 2784.doi: 10.7503/cjcu20120301

• 高分子化学 • 上一篇    下一篇

8-苯胺-1-萘磺酸钛配合物的合成及催化乙烯与降冰片烯共聚合反应

张浩1, 张贺新2, 蔡小平3, 郝秀峰4, 张学全2   

  1. 1. 北京化工大学材料科学与工程学院, 北京 100029;
    2. 中国科学院长春应用化学研究所, 长春 130022;
    3. 中国石油吉林石化分公司, 吉林 132021;
    4. 吉林大学化学学院高分子科学系, 长春 130012
  • 收稿日期:2012-04-05 出版日期:2012-12-10 发布日期:2012-11-20
  • 通讯作者: 郝秀峰,男,博士,副教授,主要从事橡胶合成等方面的研究.E-mail:haoxf@jlu.edu.cn张学全,男,研究员,主要从事橡胶合成等方面的研究.E-mail:xqzhang@ciac.jl.cn E-mail:haoxf@jlu.edu.cn;xqzhang@ciac.jl.cn
  • 基金资助:

    国家自然科学基金面上项目(批准号: 51073067)资助.

Synthesis of 8-Anilino-1-naphthalenesulfonic Titanium Complex and Ethylene-norbornene Copolymerization

ZHANG Hao1, ZHANG He-Xin2, CAI Xiao-Ping3, HAO Xiu-Feng4, ZHANG Xue-Quan2   

  1. 1. College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China;
    2. Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China;
    3. Jilin Petrochemical Co. Ltd., PetroChina, Jilin 132021, China;
    4. Department of Polymer Science, College of Chemistry, Jilin University, Changchun 130012, China
  • Received:2012-04-05 Online:2012-12-10 Published:2012-11-20

摘要:

合成了新型催化剂8-苯胺-1-萘磺酸钛配合物, 并应用于乙烯与降冰片烯的共聚合反应中. 分别考察了助催化剂种类[甲基铝氧烷(MAO)和三乙基铝(TEA)]、 降冰片烯浓度、 Al/Ti摩尔比、 聚合温度和聚合压力对催化活性与共聚性能的影响. 通过核磁共振、示差扫描量热和凝胶渗透色谱等对所制备的共聚物进行了表征. 结果表明, 在相同条件下, 以MAO为助催化剂时, 共聚催化活性更高, 催化剂为单活性中心, 可得到分子量分布较窄(PDI≈3)的共聚产物, 其共聚反应机理为加成聚合. 另外, 随着降冰片烯浓度的升高, 共聚物中降冰片烯单元的摩尔比呈线性上升趋势, 所得共聚物的熔点随之降低.

关键词: 8-苯胺-1-萘磺酸, 钛配合物, 乙烯, 降冰片烯, 共聚合反应

Abstract:

The synthesized novel 8-anilino-1-naphthalenesulfonic titanium complex was used as catalyst for ethylene and norbornene copolymerization. The polymerization behavior of synthesized titanium complex was typically studied by varying various parameters, types of cocatalyst, concentration of norbornene, Al/Ti molar ratio, polymerization temperature and pressure. The resulting copolymers were characterized by 13C NMR, DSC and GPC. It was found that when methylaluminoxane(MAO) was used as cocatalyst, the catalytic activity was higher than that of triethyl aluminum(TEA) as cocatalyst under the same condition, and the copolymerization reaction mechanism was addition polymerization. In addition, the GPC curves of the copolymers showed a unimodal with a relatively narrow molecular weight distribution(Mw/Mn≈3). The incorporation ratio of the norbornene linear increased with the increase of norbornene feed ratio, while the melting point of the resulting copolymer was decreased with the norbornene feed ratio.

Key words: 8-Anilino-1-naphthalenesulfonic acid, Titanium complex, Ethylene, Norbornene, Copolymeri-zation

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