Page 27 玩具当中过敏化合物的检测 June 2010 Phthalates analysis with 5975C GC/MSD Page 28 Sample prepartion 1g sample is put into 50ml centrifuge tube with cap
Add in 10ml Extraction solvent THF and shake 30min
Centrifuge and inject the supernatant December 22, 2011 ApplICation title 29 TIC of 40 items using DB-35ms UI T im e - -> A b u n d a n ce T IC : re a ls a m p le 0 0 5 .D \ d a ta .m sToys sample B(5ug/ml spiked) T im e - - > A b u n d a n c e T IC : re a ls a m p le 0 0 8 . D \ d a t a .m sDRS easy found taget buried by heavy background of sample B(for example:amyl cinnamaldehyde) Conclusion • DB-35ms UI is a excellent column for those compounds with active group list in 2009/48/EC
• DRS software is useful tool for fast screening allergen in toys even in very strong background interference. 34 邻苯二甲酸酯类增塑剂的GC/MS检测方法
June 2010 Phthalates analysis with 5975C GC/MSD Page 35 邻苯二甲酸酯的背景介绍 邻苯二甲酸酯（Phthalate）缩写PAEs 。是一种挥发性很低，稳定性高且 无味或具有芳香气味的粘稠液体。在水中溶解度很小，易溶于多数有机溶剂。
June 2010 Phthalates analysis with 5975C GC/MSD Page 37 常见的六种邻苯二甲酸酯类增塑剂 June 2010 Phthalates analysis with 5975C GC/MSD Page 38 Dibutyl phthalate (DBP) M.Wt 278, CAS 84-74-2 Benzyl butyl phthalate (BBP) M.Wt. 312,CAS 85-68-7 Bis- (2-ethylhexyl) phthalate (DEHP) M.Wt. 390,CAS 117-81-7 Di-n-octyl phthalate (DNOP) M.Wt. 390, CAS 117-84-0 Di-isononyl phthalate (DINP) M.Wt. 418,CAS 28553-12-0 68515-48-0 Di-isodecyl phthalate (DIDP) M.Wt. 446,CAS 26761-40-0 68515-49-1 Six regulated PAEs the most intense peak in the EI spectrum is at m/z 149, the only exception is for DMP where both R and R' are CH3 and so the H on the oxygen is replaced by CH3 and consequently m/z 163 becomes the base peak. GBT 22048-2008 玩具及儿童用品 聚氯乙烯塑料中邻苯 二甲酸酯增塑剂的测定 •将样品切至5mm x 5mm以下，准确成1g样品 •加入120mL 二氯甲烷，索氏萃取6小时 •旋转蒸发将溶剂蒸至10mL左右 •当浓缩液出现粘稠、混浊的情况下，可将浓缩液经过固相萃取柱 进行净化处理 •二氯甲烷定容至25mL， •试液经有机相微孔过滤膜后，GC/MS 上机分析
June 2010 Phthalates analysis with 5975C GC/MSD Page 41 GC/MS分析条件（ 参照国标GB/T 22048-2008 ） June 2010 Phthalates analysis with 5975C GC/MSD Page 42 GC Conditions Column: DB-5ms Ultra inert capillary column, 30 m×0.25 mm×0.25 μm (P/N 122-5532UI ) Inlet Temperature: 300°C, Spilt 20:1, split injection liner (Agilent Part no. 5188-4647). Carrier Gas: Helium, Constant Flow Mode, 1.2 mL/min Injection Volume: 1 μL, Oven Program: 180 °C for 0.5min; to 280 °C at 20 °C/min and hold for 7 min
MS Conditions Solvent Delay: 4.2 min MS Temp : 230 ºC (Source); 150 ºC (Quad) Transfer Line : 280 °C MS : EI, SIM/Scan Scan Mode : mass range (50-500 amu) SIM Mode : Ions (next slide) Sample: Five calibration solutions were prepared by dilution in DIChloromethane (DCM), the concentration range of DBP, BBP, DEHP and DNOP is from 0.5μg/mL to 10 μg/mL，and the concentration range of DINP and DIDP is from 5μg/mL to 100μg/mL in calibration solutions. 常见六种塑化剂的定性及定量离子 Phthalates analysis with 5975C GC/MSD June 2010 Page 43 TypICal quantitation ions for phthalates
No. compounds CAS No. Tgt ion Q1 Q2 Q3 1 Dibutyl phthalate (DBP) 84-74-2 149 150 223 205 2 Benzyl butyl phthalate (BBP) 85-68-7 149 091 206 238 3 Bis- (2-ethylhexyl) phthalate (DEHP) 117-81-7 149 167 279 150 4 Di-n-octyl phthalate (DNOP) 117-84-0 279 149 150 261 5 Di-isononyl phthalate (DINP) 28553-12-0 293 149 127 167 6 Di-isodecyl phthalate (DIDP) 26761-40-0 307 149 141 150 六种塑化剂的总离子流色谱图 (GB/T 22048-2008 ) Phthalates analysis with 5975C GC/MSD June 2010 Page 44 Time--> Abundance DBP BBP DEHP DNOP DINP DIDP •DBP, BBP, DEHP and DNOP, 5ppm each; •DINP and DIDP, 50ppm each DINP m/z 293 和DIDP m/z 307 的提取离子流色谱图 Phthalates analysis with 5975C GC/MSD June 2010 Page 45 Relative Abundance % Ion 307.00 (306.70 to 307.70): s4.D\DATA.MS DINP DIDP 六种塑化剂的五点校正曲线的线性 Compound Name Range of linearity (mg/L) Correlation coeffICient (R2) 1 Dibutyl phthalate 0.5 ~10 0.9992 2 Benzyl butyl phthalate 0.5 ~ 10 0.9991 3 Bis- (2-ethylhexyl) phthalate 0.5 ~ 10 0.9990 4 Di-n-octyl phthalate 0.5 ~ 10 0.9990 5 Di-isononyl phthalate 5 ~ 100 0.9986 6 Di-isodecyl phthalate 5 ~ 100 0.9979 Phthalates analysis with 5975C GC/MSD June 2010 Page 46 PVC玩具样品的GC/MS分析结果（ 参照国标GB/T 22048-2008 ） Phthalates analysis with 5975C GC/MSD June 2010 Page 47 Time--> Abundance DEHP DINP A B A：TIC of PAEs standards B: TIC of one real sample 样品中增塑剂DINP 和DEHP的含量总和为0.037 %, 低于法规限量要求(0.1%). GC/MS分析条件（ 参照CPSC ） June 2010 Phthalates analysis with 5975C GC/MSD Page 48 GC Conditions Column: DB-5ms Ultra inert column, 30 m×0.25 mm×0.25 μm,(P/N 122-5532UI ) Inlet Temperature: 290 °C， Carrier Gas: Helium at 1 mL/min Injection Mode: Splitless, pulse injection at 35 psi for 0.5 min, splitless injection liner (P/N 5188-3316). Injection Volume: 1 μL Oven Program: 50 °C for 1 min, to 280 °C at 30 oC/min, to 310 °C at 15 °C /min and hold for 4 min
MS Conditions Solvent Delay: 5 min MS Temp : 230 ºC (Source); 150 ºC (Quad) Transfer Line Temp: 280 °C MS : EI, SIM/Scan Scan Mode : mass range (50-500 amu) Sample: Five calibration solutions at 0.25, 0.5, 1, 2, 5 and 10 μg/mL were prepared by dilution in cyclohexane, along with one calibration blank (cyclohexane). Each standard solution contains 5 μg/mL of benzyl benzoate as internal standard. DIDP六针进样的重复性 from six injections at 1 ppm
June 2010 Phthalates analysis with 5975C GC/MSD Page 49 Relative Abundance% Excellent reproducibility from injection to injection 婴儿奶嘴空白样品(A)及2ppm加标样品(B)参照CPSC方 法的前处理的总离子流色谱图 Phthalates analysis with 5975C GC/MSD June 2010 Page 50 Time--> Abundance Time--> A: infant pacifier extract B: infant pacifier extract spike DMP DEP BB DBP DHP BBP DBEP DEHP DNOP DINP DIDP 如何保证数据的质量 • 当QC样品误差超过15%-20%时需进行仪器的维护 • 切色谱柱头切割10-15cm，更换衬管 • 当仪器线性/重复性不好时，需进行仪器整体维护 • 清洗进样口，更换分流平板 • 定期老化色谱柱，清洗离子源，更换分流出口管路，
GC/MS分析条件（ 参照EN-14362 ） June 2010 Phthalates analysis with 5975C GC/MSD Page 59 GC Conditions Column: DB-35ms capillary column, 30 m×0.25 mm×0.25 μm Inlet Temperature: 260°C, Spilt 10:1 Carrier Gas: Helium, Constant Flow Mode, 1.0 mL/min Injection Volume: 1 μL, Oven Program: 100°C for 2min; to 280 °C at 15 °C/min and hold for6 min, Post Run at 310 for 2min
MS Conditions Solvent Delay: 3.5min MS Temp : 230 ºC (Source); 150 ºC (Quad) Transfer Line : 280 °C MS : EI, SIM/Scan Scan Mode : mass range (50-30 amu) SIM Mode : Ions (略) 24种芳香胺和4个ISTD的SIM/SCAN总离子流色谱图 June 2010 Phthalates analysis with 5975C GC/MSD Page 60 校正曲线 June 2010 Phthalates analysis with 5975C GC/MSD Page 61 Real sample测试结果 June 2010 Phthalates analysis with 5975C GC/MSD Page 62 多溴联苯、多溴联苯醚的GC/MS检测方法
June 2010 Phthalates analysis with 5975C GC/MSD Page 63 多溴联苯、多溴联苯醚的背景介绍 • 多溴联苯醚的英文名为Poly Brominated Diphenyl Ethers（简 称PBDEs），有四溴联苯醚、五溴、六溴、八溴、十溴等209 种同系物。
有害物质的限制(RoHS) RoHS (Directive 2002/95/EC) 指令禁止在电器电 子 材料(EEE)中使用多溴联苯及多溴联苯醚 禁止使用一些有害的含溴阻燃剂化合物 (penta- BDE, octa-BDE,deca-BDE) PBDE 分析的前处理方法 June 2010 Phthalates analysis with 5975C GC/MSD Page 66 Extraction (dissolution or soxhlet extraction) Dilution GC/MS measurement Agilent method Extraction (dissolution or soxhlet extraction) Cleanup GC/MS measurement IEC method Page 67 PBDE标样的SIM/SCAN总离子流色谱图 十溴联苯醚的全扫描质谱图 June 2010 Phthalates analysis with 5975C GC/MSD Page 68 May 2007 Page 69 塑料中的多溴联苯醚的气质分析的总离子流图 GC: Inlet: S/SL 320C, Column: DB-5ms, 15m*250&mICro; m*0.1 &mICro; m, 1.7ml/min, Oven: 90C(1 min), 20C/min to 340C, hold 2 min. MS: IS, 300C, Q: 180C. May 2007 Page 70 Agilent GC-MSD的重要功能 加热质量分析器 !!! 多溴联苯及多溴联苯醚是高沸点化合物! 高离子源温度可以生成更好的峰形，更耐样品的污染，尤其是聚合物样品!! 安捷伦独特的加热四极杆技术可以防止质量分析器受到中性化合物的污染 而不加热四极杆更容易受到污染，因此增加维护的频率. MAX Source Temp MAX Quad Temp Agilent 5975 C 3500C 2000C May 2007 Page 71 十溴联苯醚的降解 Impurities in BDE209 Sample: 50ppm BDE209 Injection: On-column, track oven Column: DB-5ms, 15m*0.25mm*0.1um Oven: 90℃(1min) to 320℃(2min) at 20℃/min
BDE206 BDE209 Peak Area of BDE206/Peak Area of BDE209=~1.0% With on-column injection, BDE206 was identified as impurity in BDE209 May 2007 Page 72 进样口温度的影响 On-column Pulsed splitless, inlet temp: 240℃ Pulsed splitless, inlet temp: 300℃ Pulsed splitless, inlet temp: 280℃ Pulsed splitless, inlet temp: 260℃ Nona-BDEs from either impurities of deca-BDE or degradation of deca-BDE in split/splitless inlet Increasing inlet temperature increases the risk of decomposition!! May 2007 Page 73 脉冲/非脉冲不分流进样方式的影响 衬管玻璃毛的影响
Liner with and without Glass wool @260℃ Glass wool No glass wool Deca-BDE Degradation in inlet Glass wool in inlet liner increase risk of decomposition. May 2007 Page 75 Instrument conditions: Inlet: split/splitless, pusled splitless 260℃, Liner: detective liner without glass wool Column: DB-5HT 15m*0.25*0.1 Flow rate：Constant flow,1.8ml/min Oven: 90℃(1min) to 320℃(3min) at 20℃/min. Transferline: 300℃. Scan: 200-1000amu. Ionsource: 300℃, quads: 150℃
建议EI-Scan分析条件 May 2007 Page 76 方法稳定性测试 22nd and 92nd Injection without Glass wool Sample: 0.43g blank ABS, dissolved in 23 mL toluene. Then diluted 40-fold. BDE209 and PCB207 spiked at 50 ppm and 0.5 ppm, respectively. The sample matrix (dissolved polymer) have no signifICant effects on the determination after 70 injections. May 2007 Page 77 建议NCI-SIM分析条件 Instrument conditions: Inlet: split/splitless, pusled splitless 260℃, Liner: detective liner without glass wool Column: DB-5HT 15m*0.25*0.1 Flow rate：Constant flow,1.8ml/min Oven: 90℃(1min) to 320℃(3min) at 20℃/min. Transferline: 300℃. Scan: 200-1000amu. Ion source: 250℃, quads: 150℃ May 2007 Page 78 NCI-Scan/SIM 测定结果 May 2007 Page 79 十溴联苯醚的NCI-SIM/Scan质谱图 NCI-Scan NCI-SIM
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