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采用三检测高温尺寸排阻色谱法评估低密度聚乙烯的分子结构:深入了解支化与加工性能的相关性

High temperature-size exclusion chromatography with triple detection to assess the molecular architecture of low-density polyethylene: Insight into branching and processability correlations.

作者信息

Subbaiah Yogesha, Shanmugam Senthilkumar, Hau Qua Eng

机构信息

TASNEE Technology and Innovation Centre, R & D Laboratory, National Industrialization Company, Al Jubail, Kingdom of Saudi Arabia.

出版信息

J Sep Sci. 2024 Jan;47(2):e2300748. doi: 10.1002/jssc.202300748.

DOI:10.1002/jssc.202300748
PMID:38286729
Abstract

In this study, three commercially available low-density polyethylene (LDPE) polymers produced via a tubular reactor process, with varying melt flow rates at 190°C/2.16 kg (4.0, 1.9, and 0.75 g/10 min), have been selected and subjected to high temperature-size exclusion chromatography (SEC) analysis coupled with an infrared-5 (IR-5), viscometer (VISCO), and multiangle laser light-scattering detectors. The molecular weight (MW), MW distribution, short-chain branching (SCB), and long-chain branching parameters were investigated. It was found that MW obtained by the universal technique (∼1.57-1.7 times) and multiangle laser light-scattering detection technique is (∼1.43-1.55 times) higher than that of the conventional calibration technique, which could be attributed to structural complexity associated with LDPEs which is not clearly understood by conventional SEC mode alone. The bulk SCB per 1000 total carbon atoms estimated by IR-5 detection was found to range from 16.50 to 17.80. On the other hand, long chain branching frequency per 1000 total carbon atoms obtained by online VISCO and multiangle laser light-scattering detection ranged from 0.46 to 0.54 and 0.65 to 0.94, respectively. Further, the significance of long chain branching parameters on the polymer processing behavior was studied in correlation with rheological property (Die swell ratio).

摘要

在本研究中,选取了三种通过管式反应器工艺生产的市售低密度聚乙烯(LDPE)聚合物,它们在190°C/2.16千克(4.0、1.9和0.75克/10分钟)下具有不同的熔体流动速率,并对其进行了高温尺寸排阻色谱(SEC)分析,该分析与红外-5(IR-5)、粘度计(VISCO)和多角度激光光散射检测器联用。研究了分子量(MW)、分子量分布、短链支化(SCB)和长链支化参数。结果发现,通过通用技术获得的分子量(约为1.57 - 1.7倍)和多角度激光光散射检测技术获得的分子量(约为1.43 - 1.55倍)高于传统校准技术,这可能归因于LDPE的结构复杂性,而传统SEC模式单独无法清楚理解这种复杂性。通过IR-5检测估计的每1000个总碳原子的本体SCB范围为16.50至17.80。另一方面,通过在线VISCO和多角度激光光散射检测获得的每1000个总碳原子的长链支化频率分别为0.46至0.54和0.65至0.94。此外,还研究了长链支化参数与聚合物加工行为的相关性以及流变性能(挤出胀大比)。

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