高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (8): 1497-1502.doi: 10.7503/cjcu20160957

• 高分子化学 • 上一篇    

新型双核FI/α-二亚胺镍(Ⅱ)催化体系制备聚乙烯-b-聚(乙烯/1-辛烯)嵌段共聚物

张艺镡, 王梦雪, 张哲源, 米普科, 王婷兰   

  1. 华东理工大学材料科学与工程学院, 上海先进聚合物材料重点实验室, 超细材料制备与应用教育部重点实验室, 上海 200237
  • 收稿日期:2016-12-27 修回日期:2017-07-11 出版日期:2017-08-10 发布日期:2017-07-11
  • 通讯作者: 米普科,男,教授,主要从事高分子合成和高分子材料研究.E-mail:pkmi@ecust.edu.cn E-mail:pkmi@ecust.edu.cn
  • 基金资助:

    国家重点研发计划项目(批准号:2017YFB0306701)和上海市重点学科和重点实验室项目(批准号:B502,08DZ2230500)资助.

Polyethylene-b-poly(ethylene/1-octene) Block Copolymer Prepared via Novel Dinuclear FI/Nickel(Ⅱ) α-Diiminecatalytic Systems

ZHANG Yixin, WANG Mengxue, ZHANG Zheyuan, MI Puke, WANG Tinglan   

  1. Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
  • Received:2016-12-27 Revised:2017-07-11 Online:2017-08-10 Published:2017-07-11
  • Supported by:

    Supported by the National Key R&D Program of China(No.2017YFB0306701) and the Project of Shanghai Key Disipline and Laboratory, China(Nos.B502, 08DZ2230500).

摘要:

合成了新型双核苯氧基亚胺锆催化剂(CatB),并与α-二亚胺镍(Ⅱ)催化剂(CatA)构成催化体系,在助催化剂甲基烷氧铝(MAO)及链穿梭剂二乙基锌(ZnEt2)作用下催化乙烯与1-辛烯共聚,制备了聚乙烯-b-聚(乙烯/1-辛烯)嵌段共聚物.采用差示扫描量热法(DSC)、傅里叶变换红外光谱(FTIR)及碳核磁共振波谱(13C NMR)等方法对聚乙烯-b-聚(乙烯/1-辛烯)嵌段共聚物进行表征.结果表明,在甲苯作溶剂的1.0 MPa和50℃条件下,MAO和金属活性中心的摩尔比为300: 1;1-辛烯加入量为0.58 mol/L时,CatB/CatA/ZnEt2催化体系制备的产物中1-辛烯插入率为4.9%,DSC出现双峰,"软段"部分在聚合物链段中分布较为集中.

关键词: 嵌段共聚物, α-二亚胺镍(Ⅱ)催化剂, 苯氧基亚胺型过渡金属催化剂, 链穿梭聚合

Abstract:

A novel dinuclear phenoxyimine zirconium catalyst(CatB) was synthesized and constituted catalytic system with nickel(Ⅱ) α-diimine catalyst(CatA). The catalytic system was used for the preparation of polyethylene-b-poly(ethylene/1-octene) copolymer in the presence of co-catalyst(MAO) and chain shuttling agent diethylzinc(ZnEt2). Polymer structure was characterized by differential scanning calorimetry(DSC), Fourier transform infrared spectrophotometer(FTIR) and carbon nuclear magnetic resonance(13C NMR). The results showed that under the same condition:toluene as solvent, pressure 1.0 MPa, temperature 50℃, n(MAO)/n(CatA+CatB)=300:1, c(1-octene)=0.58 mol/L, the insert amount of 1-octene on copolymer was 4.9%. The DSC curve presented bimodal profile and the "soft" segment of the products was more concentrated.

Key words: Block copolymer, Nickel(Ⅱ) α-diimine catalyst, Phenoxyimine zirconium catalyst, Chain shuttling polymerization

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