首页   按字顺浏览 期刊浏览 卷期浏览 An Analytical Method for Long-Chain Branching in Free-Radical Polymerization of Ethylene
An Analytical Method for Long-Chain Branching in Free-Radical Polymerization of Ethylene

 

作者: Kohji Yamamoto,  

 

期刊: Journal of Macromolecular Science: Part A - Chemistry  (Taylor Available online 1982)
卷期: Volume 17, issue 3  

页码: 415-431

 

ISSN:0022-233X

 

年代: 1982

 

DOI:10.1080/00222338208056481

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

Quantitative measurements on long-chain branching in polyethylene have not been established. This paper presents a method available for calculating the degree of long-chain branching and the exponent α in the hydrodynamic relation g = Gα(where g is the ratio of the intrinsic viscosities of branched and linear molecules at the same molecular weight, and G is the corresponding ratio of mean square radii of gyration), by means of polymerization parameters, size exclusion chromatography, viscosity measurement, and amount of total unsaturation. The calculation based on our experimental data shows the following, in radical polymerization of ethylene. (1) With reaction pressure and temperature varied, the degree of long-chain branching was 0.5 to 3.7 per 1000 carbons. (2) As for the rate constant for long-chain branching, the activation energy Etrp- Epand the activation volume Δ Vtrp* - ΔVp* were 4.1 kcal/mol and 20 cc/mol, respectively. (3) The value of the exponent α, which is considered to represent the type of branching, was independent of reaction pressure and decreased with an increase of reaction temperature, and it was between 0.9 to 1.5, centering around 1.1. The validity of these values in (1), (2), and (3) and the type of branching are discussed.

 

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