聚合物样品中添加剂的在线萃取色谱分析

聚合物目前被用作热塑性树脂（通用树脂、工程塑料和超级工程塑料）和    据用途目的合成为具有性能和性能的树脂，树脂中含有的各种添加剂对提高性能和添加新的性能也至关重要。许多添加剂被用于制造抗氧化剂、紫外线吸收剂、光稳定剂、热降解抑制剂、增塑剂等。在一种产品中经常使用几种类型的添加剂，有必要分析添加剂的数量和组合的影响，并找出聚合物中随时间变化的变化、分解和作用机理。为了弄清楚它们，样品预处理、分离分析和光谱分析需要大量的时间、精力和分子结构分析。在线连接预处理和分离分析的测量方法可以期望提高包括样品预处理在内的分析的效率和精度。我们开发了在线萃取色谱系统（ex-色谱系统），它可以将SFE或溶剂萃取（在控制压力和温度下）与SFC或HPLC结合在一个系统中，并报道了使用该系统进行天然和医疗产品成分测量的应用。在本报告中，我们应用ex-色谱系统对聚合物样品中的几种添加剂进行了分析，并研究了将SFE样品预处理和HPLC分析相结合的在线测量方法。本应用中结论：Seven types of additives were extracted and separated in a short time by online SFE-HPLC. Injection volume of extracts to HPLC after online SFE influenced peak shape in this measurement. A lot of unknown peaks were eluted, and identification by UV spectra was insufficient.SFC 2018 Analysis of Additives in Polymer Samples by Online Extract i on-Chromatography System Masao Bounoshita， Akitaka Terada， Satoe lijima， Yasuyo Sato， Miki Kuwajima JASCO Corporation， 2967-5 Ishikawa-machi， Hachioji， Tokyo 192-8537 E-mail： satoe.i ijima@jasco.co.jp I n order to f i gure ou t them， plenty of t i me， effort ， and ingenui t y are required over the sample pretreatment，separation analysis， and molecular structural analysis by spectroscopy. The measurement method that connec t s pretreatment and separation analysis online can be expected to improve t he efficiency and precision of analysis i ncl u ding sample pretreatment . We have deve l oped onl i ne extraction-chromatography system (EX-Chromato System) which can be combined SFE or solvent extraction (under controlled pressu r e and temperature) with SFC or HPLC i n one system and reported applications about the measurements of ingredients i n nat u ral and medical products using this system1. 2). In th is presentation， we ap p lied the EX-Chromato System to analysis of several add i t i ves in polymer samples and i nvest i ga t ed the online measurement method combi n ing sample pretreatment by SFE w it h HPLC analysis. ·Organic solvent Ext rac tion section On li n e connect i o n Ch r omatography section SFE SFC ·Liqu i efed CO，+entrainer ·L iquiefed CO，+ modif i er I nject t h e ext r ac t to separat i on section b y s S o lven t ext r act i on ampling loop or H PLC trap col u mn · Organic solvent ● Mixed solvent of organic solvent and water ●Mixed solven t o f organ i c solvent and (wi t h addi t ive r eagents such as aci d， b asic ， water (wi t h addit i ve reagents such as ac i d，basic ， and volat i le buffer) and volatile buffer ) Fig. 1 Available extraction and chromatography on EX-Chromato System. Experimental A pp aratus The EX-Chromato System was configured u sing JASCO EXTREMA series. F i gure 2 shows the appearance of EX-Chromato System. Figure 3 shows schemat i c diagram of the system Fig .3 The schematic diagram of EX-Chromato System. Sam pl e Seven additives shown in F i g. 4 were used as standard samples. We used a weather-resistant gardening sheet and plastic shopping bag made of po l yethylene as polymer samp l es (F i g . 5). Quant i ficat i on was per f ormed using I rganox 1330 as an inter n al standard (IS)， since i t was confirmed that Irganox 1010 and Ir gafos 168 were contained in these polymer samples. Plastic shop p ing bag F i g. 5 Polymer samples. Fig.6 Gardening sheet Fig. 4 Structure of standard samples S. loaded i nto extraction vessel Sam p le Pretreatment Results and Discussion Influence of I njection Volume on HPLC after SFE F i gure 7 shows the chromatogram of standard sample measured by onl i ne SFE-HPLC . Figure 8 shows the i n f l u ence of inject i on volume on peak shape and table 3 shows the change of theoret i cal plate number and symmet r y factor by inject i on volume.As shown in t he fi gure and table.peak shape and peak parameters were deter i orated by increase in i n j ection volume. Therefore.We selected 5 pL as an i n j ect i on volume. Fig. 7 Chromatogram of standard sample (online SFE-HPLC). Table 1 Change of NTP and symmetry factor by i njection volume. Fig. 8 Change of peak shape by injection volume. Determination of addi t ives i n po lymers by onli n e SFE -HPLC Table 2 Reproducibility of retention time and Fig. 9 Chromatogram of standard Number oi Retention time Peak height ratio* injection InIrganox1010 Irgafos168 68 1 Irganox1010 一 Irgafos168 1st 13.872 20.580 0.835 1.585 13.832 20.487 0.840 1.505 13.857 20.512 0.833 1.579 13.993 20.767 0.852 1.512 13.883 20.635 0.842 1.580 6th 13.887 20.640 0.844 1.401一1.520 Average 13.887 20.604 0.841 0.0507 0.0927 0.0D6 0.073 %RSD 0.36 0.45 0.67 4.79 UV spectra of co-el u ti n g p eak with Irganox1010 Conclusion ●Seven ty p es of additives were extrac t ed and sepa r ated in a shor t t i me by online SFE-HPLC ● Inject i on vol u me of ext r act s t o HPLC afte r on li ne SFE inf l uenced p eak sha p e in t h is measurement . ● A l ot of unk n own peaks were eluted， and identification by UV spectra was insuffi ci ent. Future Tasks ● Iden ti f i cat i on of u nknown peaks by simul t aneous measurement usi n g MS and IR spect r a · E x am in at i on of recovery rate and i m provement on sampl e shape and l oading me tho d i nt o vessels a t extract i on ● Investigat i on of extrac t io n conditions and r eduction of influence on p eak shape in chromatography ·Condensation by a t rap column f or high sensi tiv e measurement References