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Citation: Niu Yan-hua, Liang Wen-bin, Zhang Yin-ling, Chen Xue-lian, Lai Shih-yaw, Li Guang-xian, Wang Du-jin. Crosslinking Kinetics of Polyethylene with Small Amount of Peroxide and Its Influence on the Subsequent Crystallization Behaviors[J]. Chinese Journal of Polymer Science, ;2016, 34(9): 1117-1128. doi: 10.1007/s10118-016-1819-z shu

Crosslinking Kinetics of Polyethylene with Small Amount of Peroxide and Its Influence on the Subsequent Crystallization Behaviors

a.
College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering of China, Sichuan University, Chengdu 610065, China
b.
Performance Material Center, National Institute of Clean-and-low-carbon Energy (NICE), Beijing 102209, China
c.
CAS Key Laboratory of Engineering Plastics, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Corresponding author: Niu Yan-hua, yhniu@scu.edu.cn
Received Date: 1 March 2016
Revised Date: 23 March 2016
Accepted Date: 23 March 2016

Fund Project: the Technical Innovation Project of National Institute of Clean and Low-Carbon Energy No. 15H0543the Open Project of State Key Laboratory of Polymer Materials Engineering of China (Sichuan University) No. sklpme2015-4-11

Crosslinking reactions of high density polyethylene with low peroxide concentrations ranging from 0.1 wt% to 1.0 wt% at temperatures of 170, 180 and 190℃ were monitored by rheological measurements. A critical gel forms at the peroxide concentration of 0.2 wt%, where the transition from long chain branching generation to crosslinking network formation could occur. Rheokinetics of crosslinking can be fitted well by Ding-Leonov’s model. The curing rate k₂ at the earlier stage exhibits about 3 times acceleration per 10℃ with increasing temperature, while the equilibrium modulus G′at the fully cured stage is almost independent of temperature. Influences of crosslinking on the subsequent crystallization behaviors were detected by DSC measurements. Above the critical gel concentration, crystallization is largely retarded as evidenced by the lower crystallization temperature T_c and crystallinity X_c due to the network formation. The secondary crystallization valley located at the temperature near 80℃ can be observed above the critical concentration, which becomes more evident with the increasing peroxide concentration and curing temperature. This phenomenon provides another evidence of crystallization retardation by the crosslinking network.
- Polyethylene,
- Rheology,
- Crosslinking kinetics,
- Crystallization
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