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    高效液相色谱法测定3D打印用塑料线材热熔时挥发的醛酮类化合物

    Determination of Aldehyde and Ketone Compounds Volatilized from Hot Melt of Plastic Wire by High Performance Liquid Chromatography

    • 摘要: 自制了一种气体采集装置收集熔融沉积成形3D打印用聚苯乙烯(ABS)、聚乳酸(PLA)、聚己内酯(PCL)等塑料线材热熔时挥发出的气体,并采用高效液相色谱法(HPLC)测定其中15种有害醛酮类气体(甲醛、乙醛、丙酮、丙醛、丁烯醛、甲基丙烯醛、丁酮、丁醛、苯甲醛、环己酮、戊醛、对甲基苯甲醛、邻/间甲基苯甲醛和己醛)含量。在自制的气体采集装置中,以50 mm·min-1的进样速率热熔10 g塑料线材,同时在经活性炭过滤后的空气的作用下,采样管中的气体以0.5 L·min-1的流量流经除臭氧管,最终到达2,4-二硝基苯肼(DNPH)衍生柱进行衍生化,用4 mL乙腈和1 mL水洗脱,洗脱液经乙腈定容后过0.45 μm滤膜,滤液供高效液相色谱分析。以Synergi MAX RP-C18色谱柱为固定相,以不同比例的乙腈和水为流动相进行梯度洗脱。结果显示:标准曲线的线性范围为0.2~2.0 mg·L-1,检出限为0.001~0.003 mg·kg-1。对PLA线材进行加标回收试验,回收率为72.0%~94.0%,测定值的相对标准偏差(n=6)为2.2%~8.6%。用此方法分析了21批次不同品牌的PLA线材、ABS线材和PCL线材,发现甲醛、乙醛的释放量较大,丙酮的检出频率较高,PLA线材和ABS线材产生的醛酮类化合物的种类和含量均高于PCL线材的。

       

      Abstract: A self-made gas collection device was used to collect the gas volatilized from hot melt of plastic wire (including ABS, PLA, PCL) used for 3D printing in the fused deposition modeling process, and the content of 15 harmful aldehyde and ketone gases (formaldehyde, acetaldehyde, acetone, propylene aldehyde, butenal, methylacrolein, butanone, butyraldehyde, benzaldehyde, cyclohexanone, glutaldehyde, p-methylbenzaldehyde, o-/m-methylbenzaldehyde, and hexanal) were determined by high performance liquid chromatography (HPLC). In the self-made gas collection device, 10 g of plastic wire were thermally melted at the injection rate of 50 mm·min-1. Under the action of air filtered by activated carbon, the gas in the collection tube flowed through the ozone-removing tube at a flow rate of 0.5 L·min-1, and finally derivatized by the 2,4-dinitrophenylhydrazide (DNPH) derivatization column. The column was eluted with 4 mL acetonitrile and 1 mL water, and the eluent was filtered through a 0.45 μm filter after making up with acetonitrile. Then the filtrate was analyzed by HPLC. Synergi MAX RP-C18 reverse-phase chromatographic column was used as the stationary phase, and the mixed solution composed of acetonitrile and water with various volume ratios was used as the mobile phase in gradient elution. The results showed that linearity ranges of the standard curves were same in the range of 0.2-2.0 mg·L-1, with detection limits in the range of 0.001-0.003 mg·kg-1. The spiked recovery was made on the PLA wire, giving recoveries in the range of 72.0%-94.0%, and RSDs (n=6) were ranged from 2.2% to 8.6%. The proposed method was used for determination of 21 batches of PLA wires, ABS wires and PCL wires of different brands, finding that the release amounts of formaldehyde and acetaldehyde were relatively larger, the detection frequency of acetone was relatively higher, and the kind and content of aldehydes and ketones produced by PLA wires and ABS wires were larger those of PCL wires.

       

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