Citation: LI Pei, ZHANG Jiaqi, LIU Wei, CHEN Quan, TANG Yujing, JI Xiangling, XUE Yanhu, SUN Guangping. Chain Structure and Properties of Four Commercial Low Density Polyethylene Resins[J]. Chinese Journal of Applied Chemistry, ;2019, 36(11): 1237-1247. doi: 10.11944/j.issn.1000-0518.2019.11.190115 shu

Chain Structure and Properties of Four Commercial Low Density Polyethylene Resins

LI Pei ^a,b ,
ZHANG Jiaqi ^a ,
LIU Wei ^a ,
CHEN Quan ^a ,
TANG Yujing ^c ,
JI Xiangling ^a ,
XUE Yanhu ^a,, ,
SUN Guangping ^b,,

a.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
College of Materials Science and Engineering, Jilin University, Changchun 130022, China
c.
Beijing Research Institute of Chemical Industry, SINOPEC, Beijing 100013, China

Corresponding author: XUE Yanhu, xueyh@ciac.ac.cn; sungp@jlu.edu.cn SUN Guangping, sungp@jlu.edu.cn
Received Date: 17 April 2019
Revised Date: 10 June 2019
Accepted Date: 26 June 2019

Fund Project: the National Natural Science Foundation 21704100Supported by the National Natural Science Foundation(No.20734006, No.50921062, No.21704100)the National Natural Science Foundation 50921062the National Natural Science Foundation 20734006

Figures(9)

Four commercial low density polyethylene(LDPE) resins with different melt flow rates were selected and their chain microstructures and the rheological properties were studied by high-temperature gel permeation chromatography(HT-GPC), ¹³carbon nuclear magnetic resonance spectroscopy(¹³C NMR), differential scanning calorimetry(DSC) and rheometer. The above resins are divided into two groups, D-1 and Q-1, D-3 and Y-1. Two resins in the same group have similar relative molecular mass. The results of ¹³C NMR spectroscopy show that the four LDPE resins not only contain short chain branches(SCB), but also have long chain branches(LCB), and the content of SCB is much higher than that of LCB, while the butyl branch in SCB is the highest one. The thermal fractionation(successive self-nucleation/annealing, SSA) results show that every resin contains different crystallizable methylene sequence lengths, i.e., the distribution of SCB in the intramolecular chain exhibits heterogeneity. The effects of molecular mass and its distribution, methylene sequence length and its distribution, branching content and crystallinity on melting behavior, rheological behavior and mechanical properties of the films were investigated. It is found that the low relative molecular mass end in Q-1 and LCB content in Y-1 influence their melt flow rate, the average methylene sequence length determines the melt temperature peaks, and the crystallinity influences the mechanical property of films. Based on the above results, the relationship between structure and property is established.
- low density polyethylene (LDPE),
- chain structure,
- rheological property,
- mechanical property
1. [1]
  XIAO Yizhi, YANG Haibin, ZHANG Qixing. Polymerization of Ethylene Catalyzed by TiCl₄/Ni(acac)₂ Supported Complex Catalysts[J]. Chinese J Appl Chem, 2001,18(7):528-531. doi: 10.3969/j.issn.1000-0518.2001.07.006
2. [2]
  Edward S W. Industrial Polymers Handbook[M]. FU Zhifeng, et al. Trans. Beijing: Chemical Industry Press, 2001(in Chinese).
3. [3]
  Gaucher-miri V, Elkoun S, Séguéla R. On the Plastic Behavior of Homogeneous Ethylene Copolymers Compared with Heterogeneous Copolymers[J]. Polym Eng Sci, 1997,37(10):1672-1683. doi: 10.1002/pen.11815
4. [4]
  Khonakdar H A, Morsheidan J. Influence of Long-Chain Branching Extent in Polyethylenes on Molecular Weight and Molecular Weight Distribution Predicted via Rheological Analysis[J]. Polym Bull, 2015,72:1217-1231. doi: 10.1007/s00289-015-1334-3
5. [5]
  Knuuttila H, Lehtinen A, Nummila-Pakarinen A. Advanced Polyethylene Technologies-Controlled Material Properties[J]. Adv Polym Sci, 2004,169:13-28.
6. [6]
  Liu J, Chen D, Wu H. Polymerization of α-Olefins Using a Camphyl α-Diimine Nickel Catalyst at Elevated Temperature[J]. Macromolecules, 2014,47(10):3325-3331. doi: 10.1021/ma5004634
7. [7]
  Randall J C. ¹³C-NMR of Ethylene-1-olefin Copolymers:Extension to the Short-Chain Branch Distribution in a Low-Density Polyethylene[J]. J Polym Sci Part B-Polym Phys, 1973,11(2):275-287. doi: 10.1002/pol.1973.180110209
8. [8]
  Galland G B, de Souza R F, Mauler R S. ¹³C-NMR Determination of the Composition of Linear Low Density Polyethylene Obtained with[η3-methallyl-nickel-diimine] PF6 Complex[J]. Macromolecules, 1999,32(5):1620-1625.
9. [9]
  Wang W J, Kharchenko S, Migler K. Triple-Detector GPC Characterization and Processing Behavior of Long-Chain-Branched Polyethylene Prepared by Solution Polymerization with Constrained Geometry Catalyst[J]. Polymer, 2004,45(19):6495-6505. doi: 10.1016/j.polymer.2004.07.035
10. [10]
  Esfahani M K, Ebrahimi N G, Khoshbakhti E. The Effect of Molecular Structure on Rheological Behavior of Tubular LDPEs[J]. Rheol Acta, 2015,54:159-168. doi: 10.1007/s00397-014-0822-y
11. [11]
  Xue Y H, Wang Y H, Fan Y D. Microstructure Characterization of Short-Chain Branching Polyethylene with Differential Scanning Calorimetry and Successive Selfnucleation/annealing Thermal Fractionation[J]. Chinese J Polym Sci, 2014,32(6)751757.
12. [12]
  Liao H Y, Qi L Y, Tao G L. Dynamic Rheological Behavior of Two LDPE/HDPE Binary Blending Melts[J]. Polym Bull, 2015,7211971205.
13. [13]
  Xu J T, Xu X, Feng L. Short Chain Branching Distributions of Metallocene-Based Ethylene Copolymers[J]. Eur Polym J, 2000,36(4):685-693. doi: 10.1016/S0014-3057(99)00128-7
14. [14]
  Fu Q, Chiu F C, He T. Molecular Heterogeneity of Metallocene Short-Chain Branched Polyethylenes and Their Fractions[J]. Macromol Chem Phys, 2001,202(6):927-932. doi: 10.1002/1521-3935(20010301)202:6<927::AID-MACP927>3.0.CO;2-K
15. [15]
  Xue Y H, Bo S Q, Ji X L. Calibration Curve Establishment and Fractionation Temperature Selection of Polyethylene for Preparative Temperature Rising Elution Fractionation[J]. Chinese J Polym Sci, 2015,33(7):1000-1008. doi: 10.1007/s10118-015-1648-5
16. [16]
  Stadler F J, Piel C, Klimke K. Influence of Type and Content of Various Comonomers on Long-Chain Branching of Ethene/α-Olefin Copolymers[J]. Macromolecules, 2006,39(4):1474-1482. doi: 10.1021/ma0514018
17. [17]
  Stadler F J, Karimkhani V. Correlations Between the Characteristic Rheological Quantities and Molecular Structure of Long-Chain Branched Metallocene Catalyzed Polyethylenes[J]. Macromolecules, 2011,44(13):5401-5413. doi: 10.1021/ma200550c
18. [18]
  Kazatchkov I B, Bohnet N, Goyal S K. Influence of Molecular Structure on the Rheological and Processing Behavior of Polyethylene Resins[J]. Polym Eng Sci, 1999,39(4):804-815. doi: 10.1002/pen.11468
19. [19]
  Xue Y H, Bo S Q, Ji X L. Molecular Chain Heterogeneity of a Branched Polyethylene Resin Using Cross-fractionation Techniques[J]. J Polym Res, 2015,22160. doi: 10.1007/s10965-015-0809-0
20. [20]
  WANG Yanfang, SU Yifan, WANG Suyu. Study on Properties of Speciality LDPE Resin for Shrink Flim[J]. China Synth Resin Plast, 2007,24(5):21-29. doi: 10.3969/j.issn.1002-1396.2007.05.006
21. [21]
  LI Dongxia, SONG Lei, WANG Hua. Structure and Properties of LDPE Resin for Heat Shrinkable Film[J]. China Synth Resin Plast, 2007,34(4):65-68.
22. [22]
  Mirabella F M. High Temperature Elution Peaks in Temperature Rising Elution Fractionation(TREF):The Behavior of High Molecular Weight Species[J]. J Liq Chromatogr Relat Technol, 2014,37(4):516-527. doi: 10.1080/10826076.2012.749494
23. [23]
  Karoglanian S A, Harrison I R. A Temperature Rising Elution Fractionation Study of Short Chain Branching Behavior in Ultra Low Density Polyethylene[J]. Polym Eng Sci, 1996,36(5):731-736. doi: 10.1002/pen.10460
24. [24]
  Xue Y H, Fan Y D, Bo S Q. Characterization of the Microstructure of Impact Polypropylene Alloys by Preparative Temperature Rising Elution Fractionation[J]. Eur Polym J, 2011,47(8):1646-1653. doi: 10.1016/j.eurpolymj.2011.05.016
25. [25]
  Hsieh E T, Tso C C, Byers J D. Intermolecular Structural Homogeneity of Metallocene Polyethylene Copolymers[J]. J Macromol Sci Phys, 1997,36(5):615-628. doi: 10.1080/00222349708220445
26. [26]
  Xue Y H, Bo S Q, Ji X L. Solvent Gradient Fractionation and Chain Microstructure of Complex Branched Polyethylene Resin[J]. J Polym Res, 2016,23131. doi: 10.1007/s10965-016-1026-1
27. [27]
  Perez C J, Failla M D, Carella J M. SSA Study of Early Polyethylenes Degradation Stages. Effects of Attack Rate, of Average Branch Length, and of Backbone Polymethylene Sequences Length Distributions[J]. Polym Degrad Stab, 2013,98(1):177-183. doi: 10.1016/j.polymdegradstab.2012.10.012
28. [28]
  Liu Y G, Bo S Q. Characterization of the Microstructure of Biaxially Oriented Polypropylene Using Preparative Temperature-rising Elution Fractionation[J]. Int J Polym Anal Charact, 2003,8(4):225-243. doi: 10.1080/10236660304880
29. [29]
  XUE Yanhu, BO Shuqin, JI Xiangling. Parameters Optimization of Successive Self-nucleation/Annealing Thermal Fractionation Experiments for Polyethylene Resin and Comparison with Step Crystallization[J]. Acta Polym Sin, 2015,3:326-330.
30. [30]
  Fillon B, Wittmann J C, Lotz B. Self-nucleation and Recrystallization of Isotactic Polypropylene (α-phase) Investigated by Differential Scanning Calorimetry[J]. J Polym Sci Part B:Polym Phys, 1993,31(10):1383-1393. doi: 10.1002/polb.1993.090311013
31. [31]
  Liu C, Zhang Z, Chen Q. Stability of Flow-Induced Precursors in Poly-1-butene and Copolymer of 1-Butene and Ethylene[J]. J Rheol, 2018,62:725-737. doi: 10.1122/1.5021000
32. [32]
  YING Qicong. Characterization of Polymer Molecular Weight Distribution as Applied to GPC Date of Polycarbonate[J]. Acta Polym Sin, 1978,1(1):17-24.
33. [33]
  Galland G B, Quijada R, Rojas R. NMR Study of Branched Polyethylenes Obtained with Combined Fe and Zr Catalysts[J]. Macromolecules, 2002,35(2):339-345. doi: 10.1021/ma010744c
34. [34]
  Randall J C, Zoepfl F J, Silverman J. A ¹³C-NMR Study of Radiation-induced Long-Chain Branching in Polyethylene[J]. Makromol Chem Rapid Commun, 1983,4(3):149-157. doi: 10.1002/marc.1983.030040307
35. [35]
  M ller A J, Arnal M L. Thermal Fractionation of Polymers[J]. Prog Polym Sci, 2005,30(5):559-603. doi: 10.1016/j.progpolymsci.2005.03.001
36. [36]
  Zhang M Q, Wanke S E. Quantitative Determination of Short-Chain Branching Content and Distribution in Commercial Polyethylenes by Thermally Fractionated Differential Scanning Calorimetry[J]. Polym Eng Sci, 2003,43(12):1878-1888. doi: 10.1002/pen.10159
37. [37]
  Vega J F, Santamaria A, Munoz-Escalona A. Small-amplitude Oscillatory Shear Flow Measurements as a Tool to Detect Very Low Amounts of Long Chain Branching in Polyethylenes[J]. Macromolecules, 1998,31:3639-3647. doi: 10.1021/ma9708961
38. [38]
  Dealy J M, Larson R G. Structure and Rheology of Molten Polymers[M]. Munich, Carl Hanser Verlag, 2006.
39. [39]
  Fetters L J, Lohse D J, Colby R H. Chain Dimensions and Entanglement Spacings[M]. In: Mark, J E, Ed. Physical Properties of Polymers Handbook, 2nd ed.; Springer: New York, 2007, Chapter 25: 445-452.
1. [1]
  Yuqi Zhai , Mengzhu Liu , Junhao Hu , Yongpeng Wang . Strengthening of Fe₃O₄/Ti₃C₂T_x MXene/CF@PANI composites with 'reinforced concrete' structure and high electromagnetic wave absorption performance. Acta Physico-Chimica Sinica, 2026, 42(10): 100248-0. doi: 10.1016/j.actphy.2026.100248
2. [2]
  Wen-Bing Hu . Systematic Introduction of Polymer Chain Structures. University Chemistry, 2025, 40(4): 15-19. doi: 10.3866/PKU.DXHX202401014
3. [3]
  Feng Zheng , Ruxun Yuan , Xiaogang Wang . “Research-Oriented” Comprehensive Experimental Design in Polymer Chemistry: the Case of Polyimide Aerogels. University Chemistry, 2024, 39(10): 210-218. doi: 10.12461/PKU.DXHX202404027
4. [4]
  Yuting Bai , Cenqi Yan , Zhen Li , Jiaqiang Qin , Pei Cheng . Preparation of High-Strength Polyimide Porous Films with Thermally Closed Pore Property by In Situ Pore Formation Method. Acta Physico-Chimica Sinica, 2024, 40(9): 2306010-0. doi: 10.3866/PKU.WHXB202306010
5. [5]
  Xiaopei HE , Jing HAN , Zhong YU , Na YE , Yi WAN . Preparation and antimicrobial properties of polyvinyl alcohol composite film based on Ag(Ⅰ) complex. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 531-542. doi: 10.11862/CJIC.20250271
6. [6]
  Ke Liu , Qi Gao , Haifeng Li , Lipeng Diao , Xuegang Chen , Daohao Li , Guanglei Wu . Hydrogen-bonding intermolecular interaction between graphene oxide and polytetrafluoroethylene enhanced creep resistance. Acta Physico-Chimica Sinica, 2026, 42(8): 100315-0. doi: 10.1016/j.actphy.2026.100315
7. [7]
  Zhaohong Zuo , Wenhao Qiu , Kehan Peng , Haowen Luo , Yihan Wang , Yunren Shi . 聚乙烯热解的AI辅助ReaxFF动力学虚拟仿真实验. University Chemistry, 2026, 41(10): 296-308. doi: 10.12461/PKU.DXHX202510010
8. [8]
  Hongli CHEN , Ziling XU , Shiwen DU , Ting WANG , Liguang WU . Controlled preparation of HKUST-1 based on polyvinylpyrrolidone and CO₂ separation performance of its doped mixed-matrix membranes. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 571-583. doi: 10.11862/CJIC.20250263
9. [9]
  Yunhan Gao , Xing Sun , Mengxia Ji , Xingchang Qiu , Tiange Wei , Qing Xu , Sheng Yin , Jiexiang Xia , Huaming Li . Hierarchical ZIF-derived carbon/Bi₁₂O₁₇Cl₂ heterostructures synergistically enhance electron dynamics and optical properties to boost CO₂ photoreduction in pure water. Acta Physico-Chimica Sinica, 2026, 42(10): 100264-0. doi: 10.1016/j.actphy.2026.100264
10. [10]
  Yupeng TANG , Haiying YANG , Fan JIN , Nan LI . Hydrogen storage properties of C₆S₆Li₆: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1827-1839. doi: 10.11862/CJIC.20240460
11. [11]
  Qiqi Li , Su Zhang , Yuting Jiang , Linna Zhu , Nannan Guo , Jing Zhang , Yutong Li , Tong Wei , Zhuangjun Fan . Preparation of High Density Activated Carbon by Mechanical Compression of Precursors for Compact Capacitive Energy Storage. Acta Physico-Chimica Sinica, 2025, 41(3): 100028-0. doi: 10.3866/PKU.WHXB202406009
12. [12]
  Yongwei ZHANG , Chuang ZHU , Wenbin WU , Yongyong MA , Heng YANG . Efficient hydrogen evolution reaction activity induced by ZnSe@nitrogen doped porous carbon heterojunction. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 650-660. doi: 10.11862/CJIC.20240386
13. [13]
  Fan Yang , Zheng Liu , Da Wang , KwunNam Hui , Yelong Zhang , Zhangquan Peng . Preparation and Properties of P-Bi₂Te₃/MXene Superstructure-based Anode for Potassium-Ion Battery. Acta Physico-Chimica Sinica, 2024, 40(2): 2303006-0. doi: 10.3866/PKU.WHXB202303006
14. [14]
  Xiaogang YANG , Xinya ZHANG , Jing LI , Huilin WANG , Min LI , Xiaotian WEI , Xinci WU , Lufang MA . Synthesis, structure, and photoelectric properties of Zinc(Ⅱ)-triphenylamine based metal-organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(10): 2078-2086. doi: 10.11862/CJIC.20250167
15. [15]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-0. doi: 10.3866/PKU.WHXB202406012
16. [16]
  Jia-Hao Wang , Bo Cai , Bowen Sun , Zhi-Ling Hou , Shu-Hao Yang , Qinglin Yang , Pei-Yan Zhao , Wen-Ping Li , Yu Zhang , Guang-Sheng Wang . Molecular dipole engineering for tailored dielectric properties in MXene/ZnO heterostructures. Acta Physico-Chimica Sinica, 2026, 42(6): 100271-0. doi: 10.1016/j.actphy.2026.100271
17. [17]
  Qiaowen CHANG , Ke ZHANG , Guangying HUANG , Nuonan LI , Weiping LIU , Fuquan BAI , Caixian YAN , Yangyang FENG , Chuan ZUO . Syntheses, structures, and photo-physical properties of iridium phosphorescent complexes with phenylpyridine derivatives bearing different substituting groups. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 235-244. doi: 10.11862/CJIC.20240311
18. [18]
  Song Zhilong , Lu Shuaihua , Zhou Qionghua , Wang Jinlan . T2MAT (text-to-material): a universal agent for generating material structures with goal properties from a single sentence. Acta Physico-Chimica Sinica, 2026, 42(5): 100213-. doi: 10.1016/j.actphy.2025.100213
19. [19]
  Yu Gao , Ye Yuan , Xiangyu Gao , Xin Bao , Yongxing Tang , Wei Huang . 综合化学实验：紫精类电致变色材料合成改进、结构表征与可视化性能探究. University Chemistry, 2026, 41(10): 239-248. doi: 10.12461/PKU.DXHX202509103
20. [20]
  Zeyi Yan , Ruitao Liu , Xinyu Qi , Yuxiang Zhang , Lulu Sun , Xiangyuan Li , Anchao Feng . Exploration of Suspension Polymerization: Preparation and Fluorescence Stability of Perovskite Polystyrene Microbeads. University Chemistry, 2025, 40(4): 72-79. doi: 10.12461/PKU.DXHX202405110

Get Citation

PDF

XML

Metrics

PDF Downloads(13)
Abstract views(3671)
HTML views(650)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142