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

Xian-feng Ji; Jian Qiu; Ming-gang Li; Hai-ping Xing; Jun Wang; Wen-bin Liu; Tao Tang

doi:10.11777/j.issn1000-3304.2017.17248

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

Research Article | 更新时间：2021-01-26

- Adjusting Melt Reaction Selectivity of Polypropylene through Nonsymmetrical Divinyl Grafting Monomers during Melt Mixing
- Acta Polymerica Sinica Vol. 5, Issue 5, Pages: 588-597(2018)
- 作者机构：
  
  1.高分子物理与化学国家重点实验室中国科学院长春应用化学研究所　长春 130022
  2.哈尔滨工程大学材料科学与化学工程学院　哈尔滨 150001
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2017.17248
  CLC：
- Published：2018-5，
  
  Received：31 August 2017，
  
  Revised：20 October 2017，
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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 5(5):588-597(2018)
DOI：

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 5(5):588-597(2018) DOI： 10.11777/j.issn1000-3304.2017.17248.

摘要

研究了具有不同双键官能团反应活性的非等活性接枝单体对于聚丙烯(PP)熔融自由基反应的影响，探索了有效调控反应选择性的途径. 首先合成了2种具有不同双键活性的非对称支化单体丙烯酸烯丁酯(BAC)、1-(烯丁氧甲基)-4-乙烯基苯(BMVB)，采用上述2种含有“非等活性双键”的多官能团化合物作为接枝单体制备长链支化聚丙烯(LCB-PP)，探索降低LCB-PP制备过程中降解和交联副反应的途径，促进长链支化结构的形成. 采用核磁、高温GPC(HT-GPC)及流变表征分析了改性样品的反应过程与支化结构. 研究发现，将上述2种非对称接枝单体应用于过氧化物引发熔融接枝反应体系时，单体中高活性的双键能够把PP大分子自由基快速转变为较稳定的自由基，抑制PP的降解；而低活性的双键与PP大分子自由基反应产生支化结构，抑制交联反应. 由于BMVB单体中高活性双键与低活性双键的竞聚率比值(17000)比BAC(2800)高，其对于自由基熔融反应过程具有更好的调控效果，表现出PP降解不明显且长支链在分子链间分布均匀.

Abstract

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

H-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.

关键词

聚丙烯自由基反应熔体反应支化结构

Keywords

PolypropyleneRadical reactionMelt reactionBranched structure

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SINOPEC Beijing Research Institute of Chemical Industry

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