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

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

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.

The synthesized novel 8-anilino-l-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.