邻苯二甲酸酯的简化评价方法

智能文字提取功能测试中

修订后的RoHS指令（欧盟）2015/863于2019年7月22日生效，限制在机械零件和玩具中使用4种邻苯二甲酸酯（见图1）。这项新指令非常严格，尤其是对于玩具中的三种邻苯二甲酸酯（DEHP、BBP和DBP），其总浓度应低于1000ppm（0.1%）。建议的邻苯二酸盐评估方法为IEC 62321-8中使用的GC/MS或Py/TD-GC/MS。然而，设置和处理这些仪器很复杂，需要更简单、更便宜的替代方案。JASCO与“Kankyo Assist Co.，Ltd”合作，使用FTIR开发了一种简化的评估方法。本申请说明提供了受控邻苯二甲酸酯的详细评估程序。采用：萃取冷凝法样品：通过萃取-冷凝法评估聚酯聚氨酯管中邻苯二甲酸酯浓度的结果如本应用本应用中结论：FTIR不能用于量化每种受限制的邻苯二甲酸酯，但可以用于量化“总”邻苯二酸酯。由于FTIR比GC/MS和Py/TD-GC/MS更快、更容易，因此它可以作为一种快速筛选技术来减少使用更复杂、更昂贵的基于MS的技术的负担。Application Note100-RF-0261 Simplified evaluationmethod of phthalates2/3Application Note Simplified evaluation method of phthalates In t rod uc tion Effec t ive 22 July， 2019， the revised RoHS directive (EU) 2015/863 restr i cted the use of 4 types of phthalates (see Figure 1) in mechanical parts as well as toys. This new directive i s ve r y st r ict， especial l y regarding the 3 types of phthalates (DEHP， BBP and DBP) i n toys ， thei r tota l concentration should be less than 1000 ppm (0.1%). The recommended evaluation method for phthalates is either GC/MS or Py/TD-GC/MS as used in IEC 62321-8. H owever， it is com p l i ca t e to set up and handle these instruments， and simpler cheaper alternative i s required. JASCO h as collaborated wi t h“Kankyo Assist Co.，Ltd”to develop a simplified eva l uation method using FTIR. This application note offers a detailed evaluation procedure for the controlled phtha l ates. Figure 1. 4 t y p e s o f pht hal a te (r estr i cted by Ro H S ) Extraction-Condensation Method Conventional l y， an FTIR spect r oscopic met h od with ATR method has b een us e d for e va l uat i ng phthalates (App Note： 100-AT -0230). Si n ce the ATR met h od does not require com p licated sam p l i ng， it offers easy sample measurement . However，th e ATR met h od does not have suf f icien t sens iti vity to reach t h e 1000 ppm (0.1%) leve l s required by the new directive.Th e r e for e ， JASCO h a s develop e d a new h i g h-sensi t i vity Ext r action -Conde n sa ti on me t hod. Using t his met h od pht h a l ates are solvent extracted f rom the s a mple， and th e n made into a thin f i lm for measurement (Figure 2). T h e LOQ (li m it of quanti t at i on) of this m e t h od is a pproxim at ely 700 ppm， and the LOD (limit of detect i ons) is a p proximat e ly 300 ppm"). I f th e pht h alat e s ar e not det e ct e d usi n g th i s method， i t can be concluded that the revised RoHS d ire ctive i s met . Since t h e m easureme n t t ime i s approx. 40 min/sample， it is estimated that more than 40 samples/day can b e analy ze d， i f m u l t i p l e sampl e s a re e xtract e d at th e same t im e. An extract i on solvent should be used that dissolves the phthalates without dissolving the resin i n the substrate. In the case of PVC resin， a mixed organic solven t (acetone ： hexane=3：7) was used. The extracted solu ti on is dropped onto a custom-made subst r ate )， wh i c h can make u niform t h in film of the sample， and then the solven t i s volatilized. The a spect r um is measu r ed of the substrate u sing a re f lect i on-absorpt i on method. The solvent for extract i on sho u l d be used wh i c h can dissolve the phthalates ， but not to dissolve the resin of substrate. In the case of PVC resin， the mixed organic solven t (acetone ： hexane=3： 7) was used. The extracted solut i on is dropped on the custom-made (substrate2) whic h can make uniform thin fi l m of sample， and the n the solvent is volatilized. The substrate is evaluated by spectrum (reflection-absorption method). Figure 2. M e a su r emen t p r o c e dur e o f e x t r a c t i o n-c o n d e n s a t ion m e t hod *1 lf the ext r acti on e ff i cie n cy of PVC resin is 70%， in t he c a s e of ot h er r esin excep t fo r PVC re s in ， t h e ve ri f i c atio n o f t h e e xtra ct ion ef f i c i enc y is r e qu i r e d *2 Thi s su bstr at e i s m a d e by K a n k y o As sist Co.， L t d . Sample Measurement The results f or eval u ation of ph th al a tes concentra ti o n from a p olyester polyu r et h ane t ub e b y ext r ac ti on -co n densat i on me th od i s detailed be l ow. 1) The sample was cut into smal l p ieces of several mm with scissors and we i ghed (Figu r e 3). The total sample weight was 1002 mg. 2) Put the sample into the mixed solvent (2 mL，acetone ： hexane=3：7)， and use ultrasonic extraction for 30 minutes. 3) Drop the extracted solution (20 pL) onto the substrate， and volatilize the solvent. 4) Measure the thin-film sample using a reflection-absorption method. 28600 Mary's C o ur t ， E asto n， MD 21601US A T el ： (800) 333-5272 F ax： (410) 822-7526A ppl ic a tio n Lib r ary： ja s c o i n c.com /appli c a t i o ns Appl i c a t i on Note Measurement Condition Ma in unit： FT/IR-4700 (l eft in Figure 4) Accessory： SMART-400i (right i n Figure 4) Detector： DLATGS Resolut i on： 4cm 1 Accumula ti o n ： 50 Figure 4. F T /I R-4700 w i th S M AR T-400i Re sults Th e sp e ct r u m in F i gu r e 5 on t h e l eft side shows t h e entir e spec tr um， and t h e sp e ct r um on th e right side s h ows a zoomed view of key band r egio n of pht h a l ates (benzene ring stretc h ing vibration ). The spectra of the actu a l sample and sta n dard ph t h a l a t e sample (1000 ppm) are overlaid in a zoomed view. As a resu l t， b enzenesul f onam i d e (plasticize r ) was d e tected，bu t phthalate was not detected. I t means t h at the sam p le meets the sta n dard of the revised RoHS direc t ive. Figure 5. I R spect r um of p ol yester p ol y ure t h a ne t ub e (e x t r actio n -c o n den s a ti o n met h od ) C onclusions FTIR cannot b e us e d to quan ti fy eac h of th e r e st r icted phthalat e s， b ut it can be used to quant i f y total'phthalat e s. Si n c e FTIR i s muc h fast e r and e asier t h an GC/MS and Py/TD-GC/MS， it can b e us e d as a rapid sc r eening t e ch n iques to r educe the bu r de n of using t h e more complex and ex p e n sive MS-based techniqu e s. Model Description Part Number Main Unit FT/IR-4700 Temperature Interval 7084-J002A Option SMART-400i Smart Tech 6909-J142A Software N/A Sampling cell (substrate forextraction-condensation method) for Smart Tech Others *1F T /I R-4700 an d F T /IR-6600/6700 a re a lso avai l a ble . *一合 2 JASCO ca n pr o vi de th e i t em a s t h e cus tomized prod u ct JASCO INC.