Citation: Hang-sheng Zhou, Kang Li, Ya-wei Qin, Jin-yong Dong. Synthesis of Long Chain-branched Polypropylene Based on Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Ziegler-Natta Catalyst[J]. Acta Polymerica Sinica, ;2019, 50(11): 1177-1186. doi: 10.11777/j.issn1000-3304.2019.19078 shu

Synthesis of Long Chain-branched Polypropylene Based on Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Ziegler-Natta Catalyst

Hang-sheng Zhou ^1,2 ,
Kang Li ^1,2 ,
Ya-wei Qin ^1,2,, ,
Jin-yong Dong ^1,2,,

1.
Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Acadamy of Sciences, Beijing 100190
2.
University of Chinese Acadamy of Sciences, Beijing 100049

Corresponding author: Ya-wei Qin, ywqin@iccas.ac.cn Jin-yong Dong, jydong@iccas.ac.cn
Received Date: 17 April 2019
Revised Date: 28 April 2019
Available Online: 11 June 2019

This study discusses a new strategy for synthesis of long chain-branched polypropylene (LCB-PP) with Ziegler-Natta catalysts, which, on the basis of conventional nonconjugated α,ω-diolefin/propylene copolymerization incapable of affording LCB, utilizes a dichlorosilane-functionalized α,ω-diolefin instead to carry out the copolymerization. Such a copolymerization with Ziegler-Natta catalysts will give PP bearing pending dichlorosilane functional groups, and it will undergo facile interchain condensations, leading to long chain-branched formation under methanol treatment and water vapor treatment. A MgCl₂/TiCl₄ catalyst containing a diether-type internal electron donor, 9,9-bis(methoxymethyl)fluorine (BMMF), was employed to catalyze di(5-hexenyl)dichlorosilane/propylene copolymerization in slurry conditions. It was found that di(5-hexenyl)dichlorosilane neither did harm to catalyst activity, nor changed the chain transfer/chain termination reaction of the original propylene polymerization. Incorporations of the mono-polymerized di(5-hexenyl)dichlorosilane were found to be between 0.02 mol% and 0.1 mol%. After the copolymerization completed, the obtained copolymers were treated with methanol or water vapor, respectively. Both the treatments could effectively transform the polymer chains-pending dichlorosilane groups into siloxane groups. The condensation degrees were distributed, which were centralized between 2 and 3 with methanol treatment. Water vapor treatment showed higher efficiency for dichlorosilane condensation than methanol treatment did. It could be found that water-treated samples exhibited systematically higher degrees of long chain-branched than their methanol-treated counterparts did with multiple evidences. Gel permeation chromatography measurement showed that the molecular weights of the copolymerized samples treated by both water vapor and methanol were improved, and the copolymers treated by water vapor in the Mark-Houwink equation curve were more deviated from the linear polypropylene than those of methanol treatment. The linear viscoelasticity of copolymers with different di(5-hexenyl)dichlorosilane concentrations after water vapor treatment and methanol treatment was investigated by means of small amplitude oscillatory shear (SAOS) to verify the existence of long chain-branched structure. According to extensional rheometry measurement, the strain hardening phenomena of the copolymers treated with water vapor were more obvious than those treated with methanol.
- Long chain-branched polypropylene,
- Nonconjugated α,ω-diolefin,
- Dichlorosilane,
- Ziegler-Natta catalyst,
- Condensation
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