顶空-气相色谱法测定异构醇聚氧乙烯醚中游离醇

doi:10.3969/j.issn.2097-2806.2023.12.016

摘要/Abstract

摘要：

建立了一种用顶空-气相色谱测定异构醇醚中游离醇含量的分析方法。采用HP-5毛细管柱（30 m×0.32 mm，0.25 µm），氢火焰（FID）检测器检测，N,N二甲基甲酰胺（DMF）为溶剂，通过优化色谱条件，确立了较优分离条件，采用保留时间定性，外标法定量，考察了方法的精密度和准确度。结果表明对于环氧乙烷（EO）加合数较高的产品具有良好的分离效果。异构十醇和异构十三醇分别在质量浓度范围为0.50~14.02 mg/mL和1.02~20.35 mg/mL时，表现出较好的线性关系，R²均大于0.999。异构十醇和异构十三醇检出限分别为0.30和0.54 mg/mL，定量限分别为0.99和1.78 mg/mL。精密度试验的相对标准偏差（RSD）中，异构十醇RSD≤0.75%，异构十三醇RSD≤0.99%。异构十醇和异构十三醇加标回收率在97.4%~104.7%之间，RSD≤2.33%（n=6）。该方法简单、准确、快速，适用于测定异构醇聚氧乙烯醚中游离醇的含量。

关键词: 顶空-气相色谱, 异构醇醚, 异构十醇, 异构十三醇

Abstract:

The free alcohols in isomeric alcohol polyoxyethylene ethers were analyzed by headspace gas chromatography （headspace GC）. Headspace GC was performed with an HP-5 column （30 m×0.32 mm, 0.25 µm） and an FID detector. DMF was used as solvent. Through optimization of equilibrium temperature, equilibrium time and sample volume, the best GC detection conditions were found. The retention time was used for qualitative analysis and the external standard method was used for quantitative analysis. The test results showed that isodecyl alcohol was a mixture of two different alcohols, and isotridecyl alcohol was a mixture of alcohols with different carbon chain length and different degree of branching. The results showed that the calibration curves of isodecyl alcohol and isotridecyl alcohol were linear in range of 0.50-14.02 mg/mL and 1.02-20.35 mg/mL with linear correlation coefficients of 0.999 3 and 0.999 1, LODs of 0.30 and 0.54 mg/mL, and LOQs of 0.99 and 1.78 mg/mL, respectively. In the precision test, the RSD for isodecyl alcohol was≤0.75% and the RSD for isotridecyl alcohol was≤0.99%. The recovery of isodecyl alcohol and isotridecyl alcohol was from 97.4% to 104.7%, with RSD≤2.33% （n=6）. It could be found that the fluctuation in detection data of isodecyl alcohol ethoxylate was slight, while that of isomeric tridecanol ethoxylate was bigger. To reduce data fluctuation, the sample weight could be increased to make the peaks more obvious when detecting isotridecanol polyoxyethylene ether. This method was simple, accurate, rapid, highly sensitive, and suitable for the determination of free alcohols in isomeric alcohol polyoxyethylene ethers.

Key words: headspace gas chromatography, isomeric alcohol polyoxyethylene ether, isodecyl alcohol, isotridecyl alcohol

中图分类号:

TQ658

梁盟, 张威, 滕晓光. 顶空-气相色谱法测定异构醇聚氧乙烯醚中游离醇[J]. 日用化学工业（中英文）, 2023, 53(12): 1472-1476.

Meng Liang, Wei Zhang, Xiaoguang Teng. Determination of free alcohols in isomeric alcohol polyoxyethylene ethers by headspace gas chromatography[J]. China Surfactant Detergent & Cosmetics, 2023, 53(12): 1472-1476.

图/表 3

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表 2

参考文献 13

[1]	Chen Ling. Study on the synthesis and properties of isomeric fatty alcohol polyoxyethylene ether and theira derivatives[D]. Wuxi: Jiang Nan University, 2012.
[2]	Huang Zhongduan, Lv Jale, Kang Wenqian, et al. Structure-property relationship in the series of iso-tridecanol polyoxyethylene ethers and their derivatives terminated with polyoxypropylene (3) block[J]. China Surfactant Detergent & Cosmetics, 2019, 49 (4) : 220-247.
[3]	Zhao Yang, Geng Jingkun, Gao Yi. Application of isomeric fatty alcohol polyoxyethylene ether in high concentration laundry detergent[J]. China Cleaning Industry, 2012 (6) : 32-36.
[4]	Zhang Qinghong, Li Yunling, Song Yongbo, et al. Prooerties of branched alcohol polyoxethylene ether carboxylates[J]. Journal of Molecular Liguids, 2018 (258) : 34-39.
[5]	Li Quanwei, Li Lei. Application of isomeric fatty alcohol polyoxyethylene ether in Super concentrated detergent[J]. China Cleaning Industry, 2017 (2) : 33-37.
[6]	Wang Xiaoping, Dong Haibo, Liu Ying, et al. Application of isomeric fatty alcohol polyoxyethylene ether in concentrated wool detergent[J]. China Cleaning Industy, 2018 (8) : 38-42.
[7]	Li Yingxue, Sun Yongqiang, Zhou Jingjie, et al. Synthesis and properties of isomeric and straight-chain alcohols polyoxyethylene ethers[J]. Applied Chemical Industry, 2022, 51 (8) : 2271-2274.
[8]	Chen Xue, Chen Tidi. Study on the characteristics of nonionic surfactants of isomeric fatty alcohol polyoxyethylene ether[C]// Proceedings of the 4th Annual Academic Conference of China Textile Printing and Dyeing Auxiliary Industry. Ningbo: China Academic Journal Electronic Publishing House, 2010: 200-201.
[9]	Zhang Zaimei, Chai Jinling, Yan Li, et al. Effects of isomeric alcohols on the phase behavior and solubilization of the microemulsion systems formed by anionic surfactants[J]. Colloid Journal, 2010, 72 (2) : 183-187. doi: 10.1134/S1061933X10020067
[10]	Li Yingxue, Sun Yongqiang, Zhou Jingjie, et al. Physicochemical and application properties of C₁₃-branched and alcohol ethoxylates (BAEO) with different ethylene oxide addition numbers[J]. Journal of Molecular Liquids, 2022, 355 (6) : 26-29.
[11]	Le T N, Phan C M, Ang H M. Influence of hydrophobic tail on the adsorption of isomeric alcohols at air/water interface[J]. Asia-Pacific Journal of Chemical Engineering, 2012, 7 (2) : 250-255. doi: 10.1002/apj.v7.2
[12]	Song Guiming, Wang Yuefang, Qian Jianfang, et al. Synthesis of iso-tridecanol polyoxyethylene ether[J]. Textile Auxiliaries, 2018, 7 (6) : 26-29.
[13]	Huang Jinwen. Study on synthesis of fatty alcohol polyether with narrow range distribution, properties and application after ist phosphate esterification[D]. Tianjin: Tianjin Polytechnic University, 2002.

样品名称	样品质量/g	异构醇外加量/mg	回收率/%	RSD/%
1007	1.023 8	2.86	100.6	1.47
1009	1.019 2	0.82	97.4	1.33
1305	1.005 8	10.12	102.9	2.33
1306	1.027 0	10.12	104.7	2.19

样号	游离醇含量/（g/kg）						平均值
样号	1	2	3	4	5	6	平均值
1（1005）	109.6	109.3	109.8	109.5	110.0	109.9	109.7
2（1007）	57.8	57.5	58.1	57.7	58.3	58.0	57.9
3（1009）	36.8	36.7	36.2	36.5	36.3	36.5	36.5
4（1305）	127.6	126.9	128.1	126.3	127.7	128.5	127.3
5（1306）	92.2	92.7	93.5	93.2	91.9	93.0	92.7
6（1309）	31.4	30.2	30.0	31.5	30.8	31.0	30.8
7（XP-50）	119.4	117.8	118.5	118.9	119.0	119.5	118.7
8（XP-80）	47.7	46.9	47.3	47.2	46.5	47.0	47.1
9（XL-70）	11.8	12.2	11.7	12.1	12.0	12.2	12.0
10（XL-90）	7.4	7.1	7.5	7.3	7.2	7.5	7.3