Citation: Xian-feng Ji, Jian Qiu, Ming-gang Li, Hai-ping Xing, Jun Wang, Wen-bin Liu, Tao Tang. Adjusting Melt Reaction Selectivity of Polypropylene through Nonsymmetrical Divinyl Grafting Monomers during Melt Mixing[J]. Acta Polymerica Sinica, ;2018, 5(5): 588-597. doi: 10.11777/j.issn1000-3304.2017.17248 shu

Adjusting Melt Reaction Selectivity of Polypropylene through Nonsymmetrical Divinyl Grafting Monomers during Melt Mixing

Xian-feng Ji ^1,2 ,
Jian Qiu ¹ ,
Ming-gang Li ¹ ,
Hai-ping Xing ^1,, ,
Jun Wang ^1,, ,
Wen-bin Liu ² ,
Tao Tang ^1,,

1.
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022
2.
College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001

Corresponding author: Hai-ping Xing, hpxing@ciac.ac.cn Jun Wang, wjlwb@163.com Tao Tang, ttang@ciac.ac.cn
Received Date: 31 August 2017
Revised Date: 20 October 2017
Available Online: 1 March 2018

The preparation of LCB-PP using symmetrical multifunctional vinyl monomers as grafting monomers presents a difficulty to efficiently control side reactions, such as peroxide-initiated chain scission and branching monomer-assisted crosslinking. In this work, we synthesized two nonsymmetrical divinyl monomers, butenyl acrylate (BAC), and 1-(but-3-enyloxy)methyl-4-vinylbenzene (BMVB) containing two carbon-carbon double bonds with different reactivity ratios. These two monomers were used in melt radical reaction of PP to prepare LCB-PP. High-temperature GPC (HT-GPC) coupled with triple detectors, ¹H-NMR and rheometer were used to characterize the microstructure and melt properties of the resultant LCB-PP. The results showed that the two monomers had double function in mediating radical reaction,i.e. stabilizing macroradicals and promoting branching reaction. Owing to a much higher reactivity ratio of the high reactive vinyl to the low reactive vinyl in the BMVB monomer, the higher reactive double-bond of BMVB preferentially reacted with macroradicals to stabilize PP macroradicals quickly, while the lower reactive double-bond later reacted with macroradicals to avoid the formation of hyper-branched or even crosslinked structure and to promote therefore the formation of long chain branched structure. Thus, compared to BAC, using BMVB as a grafting monomer led to less degradation of PP and helped to the formation of more uniformly distributed LCB structure on the PP backbone. These results demonstrate that the reactivity ratio of double-bonds in a grafting monomer to macroradicals is a key factor to control melt reaction. It is believed that further optimizing chemical structure of grafting monomer with nonsymmetrical vinyl groups, especially the reactivity ratio of double-bonds in branching monomer, will be beneficial to mediating this melt reaction.
- Polypropylene,
- Radical reaction,
- Melt reaction,
- Branched structure
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