新型茂金属高支化聚乙烯产品的结构及性能研究
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摘要
采用核磁共振分析仪、差式扫描量热仪,研究了不同碳链长度极低密度聚乙烯树脂(PE-VLD)产品的支化组成分布和熔融结晶性能;分别选取了平均序列长度、相对单体分布、共聚单体竞聚率进行聚合特性分析;运用自成核退火热分级(SSA)处理,讨论了晶片厚度(L)、相对支化度(S)、结晶度(X_c)等结晶特性。结果表明,密度为0.912g/cm~3、熔体流动速率为1.0g/10min的PE-VLD产品,以己烯为共聚单体(C6)制备的产品中共聚单体含量、S低于以丁烯为共聚单体(C4)产品;而X_c、L则要高于C4产品。
The branching composition distribution and melting-crystallization properties of very-lowdensity polyethylene PE-VLD with different chain lengths were investigated by means of ~(13) C-NMR spectroscopy and differential scanning calorimetry.The polymerization characteristics of these PEVLD samples were analyzed on the basis of mean sequence lengths,relative monomer distribution and monomer reactivity ratios,and their crystallization characteristics including lamellar thickness,relative branching degree and crystallinity degree were investigated by SSA thermal classification method.The results indicated that,in the case of PE-VLD with a density of 0.912 g/cm~3 and a melt flow rate of 1.0 g/10 min,the sample synthesized by using a butylethylene comonomer exhibited a lower content of copolymerized segment and a lower branching degree than that using a butylene comonomer.However,it had higher crystallinity degree and thicker crystalline lamellas.
The branching composition distribution and melting-crystallization properties of very-lowdensity polyethylene PE-VLD with different chain lengths were investigated by means of ~(13) C-NMR spectroscopy and differential scanning calorimetry.The polymerization characteristics of these PEVLD samples were analyzed on the basis of mean sequence lengths,relative monomer distribution and monomer reactivity ratios,and their crystallization characteristics including lamellar thickness,relative branching degree and crystallinity degree were investigated by SSA thermal classification method.The results indicated that,in the case of PE-VLD with a density of 0.912 g/cm~3 and a melt flow rate of 1.0 g/10 min,the sample synthesized by using a butylethylene comonomer exhibited a lower content of copolymerized segment and a lower branching degree than that using a butylene comonomer.However,it had higher crystallinity degree and thicker crystalline lamellas.
引文
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[3]Eynde S V,Mathot V B F.Progress in Polymer Crystallization Theory[J].Polymer,2000,41(22):3411-3423.
[4]葛腾杰.极低密度聚乙烯树脂技术开发与性能研究[J].精细石油化工进展,2015,16(16):52-54.Ge Tengjie.Study on the Technology Development and Properties of Very Low Density Polyethylene Resin[J].Advances in Fine Petrochemical Industry,2015,16(16):52-54.
[5]王彦荣,景政红.1-己烯共聚与1-丁烯共聚LLDPE的性能对比[J].合成树脂及塑料,2010,27(1):71-74.Wang Yanrong,Jing Zhenghong.Comparison of Properties of 1-copolymerized with 1-butene and Copolymerized with LLDPE[J].Synthetic Resins and Plastics,2010,27(1):71-74.
[6]Randall J C.A Review of High Resolution Liquid 13 C Nuclear Magnetic Resonance Characterization of Ethylene Based Polymers[J].Polym Rev Macromol Chem Phys,1989,29(23):201-317.
[7]Seger M R,Maciel G E.Quantitative 13 C-NMR Analysis of Sequence Distributions in Poly-(ethylene-co-1-hexene)[J].Anal Chem,2004,76(19):5734-5747.
[8]Wharry S M.Randomness in Ziegler-Natta Olefin Copolymerizations as Determined by 13 C-NMR Spectroscopy the Influence of Chain Heterogeneity[J].Polymer,2004,45(9):2985-2989.
[9]Flory P J.Principles of Polymer Chemistry[M].Ithaca,NY:Cornell University Press,1953:182.
[10]王亚丽,王秀绘,王斯晗,等.1-己烯共聚物HF-7042和1-丁烯共聚物DFDA-7042性能对比[J].塑料工业,2011,39(9):66-68.Wang Yali,Wang Xiuhui,Wang Sihan,et al.Comparison of Properties of 1-copolymer HF-7042and 1-butene Copolymer DFDA-7042[J].Plastics Industry,2011,39(9):66-68.
[11]左胜武,邱敦瑞,林龙,等.乙烯-1-己烯共聚PE的微观结构与热性能[J].合成树脂及塑料,2010,27(3):63.Zuo Shengwu,Qiu Dunrui,Lin Long,et al.Microstructure and Thermal Properties of Ethylene-1-hexene Copolymer[J].Synthesis Resin and Plastics,2010,27(3):63.
[12]Czaja K,Bialek M.Microstructure of Ethylene-1-hexeneand Ethylene-1-octene Copolymers Obtained Over Ziegler-Natta Catalysts Supported on MgCl2(THF)2[J].Polymer,2001,42(6):2289-2297.
[13]Janimak J J,Stevens G C.Inter-relationships between Tie-molecule Concentrations,Molecular Characteristics and Mechanical Properties in Metallocene Catalysed Medium Density Polyethylenes[J].J Mater Sci,2001,36(8):1879-1884.
[14]杨柳,左胜武,尚小杰.茂金属线型低密度聚乙烯的结构与性能[J].合成树脂及塑料,2006,23(3):47-50.Yang Liu,Zuo Shengwu,Shang Xiaojie.Structure and Properties of Metallocene Linear Low Density Polyethylene[J].Synthetic Resin and Plastics,2006,23(3):47-50.
[15]宋士杰,冯嘉春,武培怡,等.结晶分级技术在支化聚乙烯研究中的应用[J].高分子通报,2008,11(3):15-25.Song Shijie,Feng Jiachun,Wu Peiyi,et al.Application of Crystallization Classification Technology in Branched Polyethylene Research[J].Polymer Bulletin,2008,11(3):15-25.