α-二亚胺镍(Ⅱ)催化乙烯与乙烯基三甲氧基硅烷共聚  

Copolymerization of Ethylene and Vinyl Trimethoxysilane withα-Diimine Nickel(Ⅱ)Catalysts

作　　者：张丹枫[1] 张文杰 牛犇 仝鑫 ZHANG Danfeng;ZHANG Wenjie;NIU Ben;TONG Xin(Shanghai Key Laboratory of Advanced Polymeric Materials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学材料科学与工程学院,上海市先进聚合物材料重点实验室,上海200237

出　　处：《华东理工大学学报（自然科学版）》2023年第5期639-646,共8页Journal of East China University of Science and Technology

基　　金：上海市重点学科和重点实验室项目(08DZ2230500)。

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、催化剂物质的量、铝镍元素物质的量之比(nAl/nNi)、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。采用高温核磁共振仪(NMR)、傅里叶红外光谱仪(FT-IR)和差示扫描量热仪(DSC)表征了共聚物的微观结构和熔点,采用等离子体发射光谱仪测定了共聚物中的硅含量,并采用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,当以C4为催化剂,且催化剂物质的量为5.0μmol, VTMoS浓度为0.50mol/L,n_(Al)/n_(Ni)=400,乙烯压力为1.0 MPa,聚合温度为25℃,聚合时间为1.0 h时,催化活性达到6.53×10^(5)g/(mol·h),共聚物中w(Si)为2.10%。A series ofα-diimine nickel(Ⅱ)catalysts,in the presence of ethylaluminum sesquichloride(EASC)as cocatalyst,were applied in the copolymerization of ethylene and vinyl trimethoxysilane(VTMoS).The effects of polymerization parameters,including catalyst structure,VTMoS concentration,catalyst dosage,molar ratio of Al/Ni(nAl/nNi),ethylene pressure,reaction time and solvent on the copolymerization were investigated.The optimized catalytic reaction conditions were obtained.High temperature NMR(Nuclear Magnetic Resonance),Fourier infrared spectroscopy(FT-IR)and differential scanning calorimetry(DSC)were used to characterize the microstructures and melting points of the copolymers.Inductively coupled plasma(ICP)was applied to determine the silicon content of the copolymers.Equilibrium swelling method was used to study the crosslinking degree of copolymers.The results showed that the catalytic activity of C4 reached 6.53×10^(5) g/(mol·h)under the optimal conditions:Catalyst dosage was 5.0μmol,c(VTMoS)=0.5 mol/L,n_(Al)/n_(Ni)=400,p(C_(2)H_(4))=1.0 MPa,T=25℃,t=0.5 h.The mass fraction of silicon in the copolymer was 2.10%.

关 键 词：α-二亚胺镍催化剂 乙烯 乙烯基三甲氧基硅烷 共聚 功能化聚烯烃 

分 类 号：O631[理学—高分子化学] O614.81[理学—化学]