聚烯烃弹性体的结构与熔体黏度关系的研究

doi:10.19491/j.issn.1001-9278.2018.09.011

中国塑料 ›› 2018, Vol. 32 ›› Issue (09): 64-70.DOI: 10.19491/j.issn.1001-9278.2018.09.011

聚烯烃弹性体的结构与熔体黏度关系的研究

赵根根,郑征,张明轩,胡倩,李伯耿

浙江大学

收稿日期:2018-04-11 修回日期:2018-05-04 出版日期:2018-09-26 发布日期:2018-10-25
基金资助:
高性能热塑性弹性体制备及加工应用中的科学问题研究;多相多组分聚烯烃产品在聚合过程中的结构调控

Study on Relationship Between Structure and Melt Viscosity of Polyolefin Elastomer

Received:2018-04-11 Revised:2018-05-04 Online:2018-09-26 Published:2018-10-25

摘要/Abstract

摘要： 采用凝胶渗透色谱仪和核磁共振仪表征了一系列聚烯烃弹性体（POE）样品的结构，并用毛细管流变仪考察了其挤出稳定性、剪切依赖性和黏温依赖性，分析了熔体黏度与聚合物结构的关系。结果表明，随着剪切速率的提高，高相对分子质量的POE熔体易出现不稳定流动，挤出物表面发生畸变；相对分子质量越大、温度越低、共聚单体含越高，发生不稳定流动的临界剪切速率c越低；POE的剪切黏度很大程度上受相对分子质量的影响，与共聚单体的含量关系不大；不同相对分子质量及组成的POE熔体的黏流活化能相近，约为2.8×10^4 J/mol。基于Carreau、Cross和Arrhenius等方程，分别建立了关联熔体零切黏度与聚合物重均相对分子质量和温度关系的半经验式、关联熔体表观黏度与零切黏度和剪切速率关系的半经验式；两式可用于预测POE熔体的黏度，其适用范围为温度为130~190 ℃，剪切速率为10~2 000 s-1，重均相对分子质量（Mw）为4.2×10^4~1.24×10^5 g/mol。

Abstract: The chain structure of several polyolefin elastomer (POE) samples was characterized by GPC and NMR, and their melt flow stability at high extrusion rate and their melt viscosities at various shear rates and temperatures were investigated by capillary rheometer. The relationship between the chain structure and melt viscosity were further analyzed. The results indicated that there was an unstable flow in the polymer melt with higher molecular weight with an increase of shear rate, and the surface of the melt extrudate became distorted. The critical shear rate also becomes lower if the molecular weight and co-monomer content were higher and the temperature was lower. The shear viscosity of POE was greatly influenced by the molecular weight and was almost not related to the co-monomer content. The polymer melts with various molecular weights and their compositions have the approximately same viscous flow activation energy around 2.8×10^4 J/mol. Based on the Carreau Equation, Cross Equation and Arrhenius Equation, the semi-model correlated with the zero shear viscosity, weight-average molecular weight and temperature and the semi-model related to correlated with the melt apparent viscosity, zero shear viscosity and shear rate were established. Both of the two equations are available to predict the melt viscosity of POE in the temperature range of 130~190 ℃, in the shear rate range of 10~2 000 s-1, in the weight-average molecular weigh range of 4.2×10^4 ~1.24×10^5 g/mol.

赵根根郑征张明轩胡倩李伯耿. 聚烯烃弹性体的结构与熔体黏度关系的研究[J]. 中国塑料, 2018, 32(09): 64-70.

参考文献

[1] 李伯耿, 张明轩, 刘伟峰,等. 聚烯烃类弹性体——现状与进展[J]. 化工进展, 2017, 36(9):3135-3144.
LI B G, ZHANG M X, LIU W F, et al. State-of-the-art and Research Progress of Polyolefin-based Elastomer[J]. Chemical Industry & Engineering Progress, 2017, 36(9):3135-3144.
[2] KARIMKHANI V, AFSHAR-TAROMI F, POURMAHDIAN S, et al. Revisiting the Long-chain Branch Formation Mechanism in Metallocene Catalyzed Polyethylenes[J]. Polymer Chemistry, 2013, 4(13): 3774-3790.
[3] CHUM P S, KRUPER W J, GUEST M J. Materials Properties Derived from INSITE Metallocene Catalysts[J]. Advanced Materials, 2000, 12(23): 1759-1767.
[4] BUBECK R A. Structure–property Relationships in Metallocene Polyethylenes[J]. Materials Science and Engineering: R: Reports, 2002, 39(1): 1-28.
[5] BIN WADUD S E, BAIRD D G. Shear and Extensional Rheology of Sparsely Branched Metallocene-catalyzed Polyethylenes[J]. Journal of Rheology, 2000, 44(5): 1151-1167.
[6] YANG K, YU W, ZHOU C. Thermal Oxidation of Metallocene Catalyzed Poly(ethylene octene) by a Rheological Method[J]. Journal of Applied Polymer Science, 2007, 105(2):846–852.
[7] 赵建才. EPDM橡胶的流变特性实验研究[J]. 弹性体, 2006, 16(4):11-13.
ZHAO J C. Experimental Study on Rheological Properties of EPDM Compound in a Capillary Rheometer[J]. China Elastomerics, 2006, 16(4):11-13.
[8] 董文武, 黄中瑛, 蒋琦. 用毛细管流变仪测量橡胶的工艺性能[J]. 世界橡胶工业, 2011, 38(7):42-45.
DONG W W, HUANG Z Y, JIANG Q. Capillary Rheometer Measurement of Rubber Process Performance[J]. World Rubber Industry, 2011, 38(7): 42-45.
[9] 张娜, 王宁, 赵贝,等. 限定几何构型茂金属催化聚烯烃弹性体EPDM Nordel IP的高速流变性能[J]. 弹性体, 2008, 18(1): 4-9.
ZHANG N, WANG N, ZHAO B, et al. The High Speed Rheological Behavior of EPDM Nordel IP Produced by CGC and INSITE Technology[J]. China Elastomerics, 2008, 18(1): 4-9.
[10] 金日光. 关于热塑性弹性体(SBS)流变学性能的研究[J]. 北京化工大学学报(自然科学版), 1979, (2): 24-43.
JIN R G. The Research on Rheological Properties of Thermoplastic Elastomers (SBS)[J]. Journal of Beijing University of Chemical Technology, 1979(2): 24-43.
[11] 张娜, 慕晶霞, 王宁,等. 限定几何构型茂金属催化POE高速流变性能[J]. 现代塑料加工应用, 2007, 19(5): 47-50.
ZHANG N, MU J X, WANG N,et al. Rheological Behavior at High Extrusion Rate of POE Produced by CGC and INSITETM Technology[J]. Modern Plastics Processing and Applications, 2007, 19(5):47-50.
[12] ASTM D50 1 7-96(2009)e1. Determination of Linear Low Density Polyethylene(LLDPE) Composition by Carbon-13 Nuclear Magnetic Resonance[S]. ASTM：West Conshohocken, PA, 2009, V01.08.02.
[13] 吴其晔, 李鹏, 王宁,等. 熔体流变曲线特征与挤出畸变的关系[J]. 现代塑料加工应用, 2013, 25(4):53-56.
WU Q Y, LI P, WANG N, et al. Relationship Between Rheological Curves and Extrudate Distortions of Polymer Melts[J]. Modern Plastics Processing and Applications, 2013, 25(4):53-56.
[14] 吴其晔, 巫静安. 高分子材料流变学[M]. 北京：高等教育出版社, 2002:38-42.
WU Q Y, WU J A. Rheology of Polymer Materials[M]. Beijing: China Higher Education Press, 2002: 38-49.
[15] VINOGRADOV G V, MALKIN A Y. Polymer Rheology[M]. Moscow: Khimiya, 1977: 71-72.

聚烯烃弹性体的结构与熔体黏度关系的研究

Study on Relationship Between Structure and Melt Viscosity of Polyolefin Elastomer

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 0

编辑推荐

Metrics

本文评价