目的: 建立同时测定药用硅橡胶管、硅橡胶垫片中六甲基环三硅氧烷(D3)、八甲基环四硅氧烷(D4)、十甲基环五硅氧烷(D5)、十二甲基环六硅烷(D6)、十四甲基环七硅氧烷(D7)、十六甲基环八硅氧烷(D8)、十八甲基环九硅氧烷(D9)含量的气相色谱法。方法: 采用HP-INNOWAX毛细管气相色谱柱(30 m×0.32 mm,0.50 μm),柱温为程序升温,进样口温度230 ℃,氢火焰离子化检测器(FID)温度250 ℃,载气N2,流速1.0 mL·min-1,分流比20∶1,进样量1 μL。结果: 在选定的色谱条件下,7种挥发性甲基环硅氧烷分离良好,且峰面积与质量浓度呈良好的线性关系(相关系数r均大于0.999 0)。D3~D9的平均回收率分别为97.0%、101.4%、97.7%、97.7%、101.7%、100.7%、102.3%。结论: 经方法学验证,本法简便,准确、专属性强,适用于药用硅橡胶管、硅橡胶垫片中挥发性甲基环硅氧烷的检测。
Objective: To establish a GC method for the determination of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcycloheptasiloxane (D7), hexadecamethylcyclooctasiloxane (D8) and octadecamethylcyclononasiloxane (D9) in medical silicone rubber tubes and gaskets. Methods: The chromatographic separation was carried out on the HP-INNOWAX capillary column (30 m×0.32 mm, 0.50 μm). Programmed temperature was applied. The inlet temperature was 230 ℃ and FID detector temperature was 250 ℃. The flow rate of carried gas (N2) was 1.0 mL·min-1 and the split ratio was 20∶1. The injection volume was 1 μL. Results: Under this specific condition, the seven dimethylcyclosiloxane volatiles were well separated and showed good linear relationships between the peak area and the concentration (r > 0.999 0). The average recoveries of D3-D9 were 97.0%, 101.4%, 97.7%, 97.7%, 101.7%, 100.7% and 102.3%, respectively. Conclusion: The method is simple, specific, accurate and suitable for analyzing the residual dimethylcyclosiloxane volatiles in medical silicone rubber tubes and gaskets.
[1] 赵陈超,章基凯.硅橡胶及其应用[M].北京:化学工业出版社, 2015:14
ZHAO CC, ZHANG JK. Silicone Rubber and Its Applicatin [M].Beijing:Chemical Industry Press, 2015:14
[2] 唐乃美.我国硅橡胶产业现状及发展建议[J].中国石油和化工经济分析, 2015 (2):54
TANG NM. Current situation and development suggestion of silicone rubber industry in China [J].Econ Anal China Pet Chem Ind, 2015 (2):54
[3] 贺炳慧,陈宏愿,张辉珍,等.食品接触材料用硅橡胶检测研究进展[J].食品安全质量检测学报, 2016, 7 (3):1183
HE BH, CHEN HY, ZHANG HZ, et al. Research progress on detection of food contact silicone rubber [J].J Food Saf Qual, 2016, 7 (3):1183
[4] 许莉,腾雅娣,华远达,等.硅橡胶的研究与应用进展[J].特种橡胶制品, 2007, 28 (1):55
XU L, TENG YD, HUA YD, et al. Research and development of silicone rubber [J].Spec Purp Rub Prod, 2007, 28 (1):55
[5] 王荣华,李晖,李倩倩,等.实验室烘箱加速老化下硅橡胶的存储寿命预测[J].合成材料老化与应用, 2013, 42 (1):1
WANG RH, LI H, LI QQ, et al. Storage life prediction of silicone rubber by laboratory accelerated aging test [J].Synth Mater Aging Appl, 2013, 42 (1):1
[6] 郭兵,麻景龙,宋晓云,等.食品接触用硅橡胶的寿命及环硅氧烷和蒸发残渣检测研究进展[J].有机硅材料, 2016, 30 (1):75
GUO B, MA JL, SONG XY, et al. Research progress on life of silicone rubber for food contact and detection of cyclosiloxane and evaporation residue [J].Silic Mater, 2016, 30 (1):75
[7] 侯锐,黄越,伍换,等.硅胶在食品接触材料的应用及安全风险分析[J].现代食品, 2015 (23):77
HOU Y, HUANG Y, WU H, et al. The application of silicone in food contact materials and safety risk analysis [J].Mod Food, 2015 (23):77
[8] SIDDIQUI WH, STUMP DG, PLOTZKE KP, et al. A two-generation reproductive toxicity study of octamethylcyclotetrasiloxane (D4) in rats exposed by whole-body vapor inhalation [J] . Reprod Toxicol, 2007, 23 (2):202
[9] VELICOGNA J, RITCHIE E, PRINCZ J, et al. Ecotoxicity of siloxane D5 in soil [J].Chemo, 2012, 87 (1):77
[10] 国家药品监督管理局药品审评中心.化学药品注射剂生产所用的塑料组件系统相容性研究技术指南(试行) [EB/OL].(2020-10-21) [2020-12-23].http://www.cde.org.cn/news.do?method=viewInfoCommon&id=25e20e27564a85cf
CDE. Guidelines of evaluating compatibility between plastic assembly system for production and pharmaceutical injections (trail) [EB/OL]. (2020-10-21) [2020-12-23].http://www.cde.org.cn/news.do?method=viewInfoCommon&id=25e20e27564a85cf
[11] 姚羽,张琳,白沧源.注射用哌拉西林钠他唑巴坦钠中外源性环硅氧烷类化合物的检测[J].中南药学, 2017, 15 (8):1114
YAO Y, ZHANG L, BAI CY. Determination of exogenous cyclosiloxanes in piperacillin sodium and tazobactam sodium for injection [J].Cent South Pharm, 2017, 15 (8):1114
[12] 刘宜奇,胡长鹰,商贵芹,等.食品接触用硅橡胶中3种环硅氧烷的测定及迁移规律[J].食品工业科技, 2020, 41 (11):245
LIU YQ, HU CY, SHANG GQ, et al. Determination and migration of three kinds of cyclosiloxanes in food contact silicone rubber [J].Sci Technol Food Ind, 2020, 41 (11):245
[13] 何毅华,王华,刘金子.气质联用法测定橡塑制品中二甲基硅氧烷[J].化工设计通讯, 2017, 43 (6):127
HE YH, WANG H, LIU JZ. Determination of dimethyl siloxane in rubber and plastic products by GC-MS [J].Chem Eng Des Commun, 2017, 43 (6):127
[14] 颜敏,刘园园,王栖,等.气相色谱-质谱联用法测定避孕套中聚二甲基硅氧烷聚合物的残留物[J].中国计划生育学杂志, 2019, 27 (6):695
YAN M, LIU YY, WANG Q, et al. Determination of polydimethylsiloxane polymer residues in condom silicone oil lubricants by GC-MS [J].Chin J Fam Plan, 2019, 27 (6):695
[15] 马玉楠,蔡弘,骆红宇. 药品与包装相容性理论与实践[M].北京:化学工业出版社, 2019:428
MA YN, CAI H, LUO HY. Theory and Practice Compatibility of Pharmaceutical Products and Packaging [M].Beijing:Chemiccal Industry Press, 2019:428
[16] GB/T 28112-2011 硅橡胶中挥发性甲基环硅氧烷残留量的测定[S].2011
GB/T 28112-2011 Determination of Residual Dimethylcyclosiloxane Volatiles in Silicone Rubber [S].2011
[17] ASTM F2466-10 Standard Practice for Determining Silicone Volatiles in Silicone Rubber for Transportation Applications [S].2018
