羟基封端聚丁二烯的临界点色谱定量方法研究

doi:10.3724/SP.J.1123.2019.03042

色谱 ›› 2020, Vol. 38 ›› Issue (2): 238-243.DOI: 10.3724/SP.J.1123.2019.03042

羟基封端聚丁二烯的临界点色谱定量方法研究

汪明芳¹, 贾强强¹, 王月荣¹, 章弘扬¹, 张敏², 胡坪¹^,^*()

¹ 上海市功能性材料化学重点实验室, 华东理工大学化学与分子工程学院, 上海 200237
² 上海市新药设计重点实验室, 华东理工大学药学院, 上海 200237

收稿日期:2019-03-30 出版日期:2020-02-08 发布日期:2020-12-10
通讯作者: 胡坪
作者简介:胡坪.Tel:(021)64252844, E-mail:huping@ecust.edu.cn
基金资助:
国家自然科学基金(81973285)

Determination of hydroxy terminated polybutadiene in the blends by liquid critical condition chromatography

WANG Mingfang¹, JIA Qiangqiang¹, WANG Yuerong¹, ZHANG Hongyang¹, ZHANG Min², HU Ping¹^,^*()

¹ Shanghai Key Laboratory of Functional Materials Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China
² Shanghai Key Laboratory of New Drug Design, School of Pharmacy, East China University of Science and Technology, Shanghai 200237, China

Received:2019-03-30 Online:2020-02-08 Published:2020-12-10
Contact: HU Ping
Supported by:
National Natural Science Foundation of China(81973285)

摘要/Abstract

摘要：

为建立混合物中羟基封端聚丁二烯（HTPB）的临界点色谱定量方法，以C18为固定相，考察了HTPB在四氢呋喃-乙腈和四氢呋喃-水两种流动相体系下的临界点色谱条件。结果表明，四氢呋喃-乙腈体积比为70.7：29.3以及四氢呋喃-水体积比为92：8时，HTPB的保留值与其相对分子质量无关。将该临界点色谱方法用于胶黏剂混合组分中HTPB的测定，结果表明，HTPB在46.7~216.4 mg/L范围内呈良好线性关系，相关系数（r）>0.99，检出限为4.2 mg/L。自配HTPB和矿物油双组分样品的加标回收率为89.2%~101.1%，相对标准偏差小于0.66%（n=6）。应用该方法对市售聚氨酯胶黏剂进行检测，测定结果为HTPB成分占26.6%。该方法快速、准确，能满足聚合物混合产品的生产质量控制和失效分析的要求。

关键词: 临界点色谱, 羟基封端聚丁二烯, 胶黏剂, 定量分析

Abstract:

A method based on liquid critical condition chromatography (LCCC) was established for the quantification of hydroxy-terminated polybutadiene (HTPB) in polymer blends. The critical conditions for HTPB were investigated using a C18 column as the stationary phase, and tetrahydrofuran (THF)-acetonitrile (ACN) or THF-water as the mobile phase. Irrespective of the relative molecular mass, HTPB was eluted under the critical conditions of THF-ACN (70.7:29.3, v/v) or THF-water (92:8, v/v). Under the optimal conditions, the HTPB exhibited satisfactory linearity in the range of 46.7-216.4 mg/L, with a correlation coefficient (r) of 0.997. The limit of detection reached 4.2 mg/L. The recoveries of HTPB from the prepared mixtures of HTPB and mineral oil ranged from 89.2% to 101.1%, with a relative standard derivation of less than 0.66% (n=6). This method was successfully applied to the quantitative analysis of HTPB in a commercial polyurethane adhesive, and 26.6% of HTPB was detected in the product. This LCCC method is simple, convenient, highly selective, and reliable for quality control and failure studies of formulated products.

Key words: liquid critical condition chromatography(LCCC), hydroxy terminated polybutadiene(HTPB), adhesive, quantitative analysis

汪明芳, 贾强强, 王月荣, 章弘扬, 张敏, 胡坪. 羟基封端聚丁二烯的临界点色谱定量方法研究[J]. 色谱, 2020, 38(2): 238-243.

WANG Mingfang, JIA Qiangqiang, WANG Yuerong, ZHANG Hongyang, ZHANG Min, HU Ping. Determination of hydroxy terminated polybutadiene in the blends by liquid critical condition chromatography[J]. Chinese Journal of Chromatography, 2020, 38(2): 238-243.

图/表 5

图1 窄相对分子质量分布的HTPB在用不同比例(a)四氢呋喃和乙腈、(b)四氢呋喃和水为流动相时的保留行为

Fig. 1 Retention behavior of narrowly distributed hydroxyl terminated polybutadiene (HTPB) using tetrahydrofuran (THF)-acetonitrile (ACN) and THF-water in different ratios as the mobile phases Peak relative molecular mass (Mp): 13330, 7828, 2595, and 1362 Da.

图2 四氢呋喃溶剂空白和宽分布HTPB的临界点色谱图

Fig. 2 Chromatograms of THF blank and broadly distributed HTPB under the critical conditions

图3 宽相对分子质量分布HTPB与矿物油混合物的色谱分析图

Fig. 3 Chromatograms of a mixture of broadly distributed HTPB and mineral oil a. size exclusion chromatography (SEC); b. liquid critical condition chromatography (LCCC).

表1 在HTPB和矿物油混合物中HTPB组分的平均加标回收率和相对标准偏差(n=6)

Table 1 Average spiked recoveries and RSDs of HTPB in the blends of HTPB and mineral oil (n=6)

Sample	Spiked level/ (mg/L)	Recovery/%	RSD/%
Blends of HTPB and oil	9.5	89.2	0.64
Blends of HTPB and oil	30.9	98.5	0.49
	73.7	101.1	0.66

表2 LCCC和1H-NMR两种方法对HTPB和矿物油混合物以及未知样品中HTPB含量的测定(n=3)

Table 2 Determination of HTPB in the blends of HTPB and mineral oil and an unknown sample by LCCC and 1H nuclear magnetic resonance spectra (1H-NMR) methods(n=3)

Sample	LCCC		Relative error of LCCC and real content/%	¹H-NMR		Relative error of ¹H-NMR and real content/%
Sample	HTPB/%	RSD/%	Relative error of LCCC and real content/%	HTPB/%	RSD/%	Relative error of ¹H-NMR and real content/%
-: the value is not available for unknown sample.
Blends of HTPB and mineral	26.8	1.4	3.1	38.7	1.6	48.8
oil (26:74, v/v)
Unknown sample	26.6	1.2	-	41.8	2.1	-

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羟基封端聚丁二烯的临界点色谱定量方法研究

Determination of hydroxy terminated polybutadiene in the blends by liquid critical condition chromatography

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