三种应用场景中聚乙醇酸低聚物的迁移和形成机理研究  

Study on Migrants and Formation Mechanism of Polyglycolic Acid Oligomers in Three Distinct Application Scenarios

作　　者：刘胜峰 梁进欣 尹甜[1] 陈胜 段逸品 董犇 李丹 钟怀宁 LIU Sheng-feng;LIANG Jin-xin;YIN Tian;CHEN Sheng;DUAN Yi-pin;DONG Ben;LI Dan;ZHONG Huai-ning(China Shenhua Coal-to-Oil and Chemical Company,Beijing 100011,China;National Reference Laboratory for Food Contact Material(Guangdong),Guangzhou Customs Technology Center,Guangzhou 510623,China)

机构地区：[1]中国神华煤制油化工有限公司,北京100011 [2]广州海关技术中心,国家食品接触材料检测重点实验室(广东),广东广州510623

出　　处：《质谱学报》2025年第2期224-232,I0005,共10页Journal of Chinese Mass Spectrometry Society

基　　金：国家能源集团2030重大项目先导项目(GJNY2030XDXM-19-15.4);广州海关科研项目(2021GZCK 22)。

摘　　要：聚乙醇酸(poly glycolic acid,PGA)是一种生物可降解聚合物,具有良好的性能。但是,用作食品接触材料时,需关注PGA中乙醇酸低聚物迁移至食品中的风险。本文建立了超高效液相色谱-串联四极杆飞行时间质谱(UHPLC-QTOF MS)法筛查分析食品模拟液中PGA低聚物,并研究PGA样品在低温食品的包装容器或器具、短期储存的热罐装一次性容器以及热饮餐具及容器3种应用场景中在酸性食品、非酸性食品和含酒精饮料中的迁移情况。结果表明,当PGA样品用作低温食品包装容器时,在食品模拟物4%乙酸、10%乙醇和50%乙醇中均未检出PGA低聚物;而用作短期热罐装和热饮餐具及容器时,在3种食品模拟物中均检出多种线性低聚物及环状低聚物,且线性GA5-GA8和cyclic GA6-cyclic GA8的迁移量较高。上述低聚物可能的形成机理是:PGA的非结晶区是无定形状态,水分子逐渐扩散后酯键开始断裂,将链段断裂为长链低聚物,长链低聚物经过多次断裂降解为短链低聚物。由于短链低聚物的分子质量较小,更容易在非结晶区域迁移到模拟液中,同时短链低聚物能够自我重组,从无序状态到有序状态,容易形成链状和环状的低聚物。本研究表明,温度对PGA样品中低聚物的形成影响较大,应用场景温度越高,检出的低聚物种类越多且迁移量越高。因此,用PGA材料及其制品在高温场景下储存酸性食品、非酸性食品及含酒精饮料时,需要关注低聚物的迁移情况。Poly(glycolic acid)(PGA)is an environmentally friendly,biodegradable polymer commonly utilized in biomedical applications.Due to its high thermal deformation temperature,favorable mechanical properties,and effective gas barrier capabilities,PGA has potential application as food contact materials.However,current regulations do not explicitly involve the use of PGA in food contact applications,particularly the migration of oligomers.The potential migration of oligomers from PGA into food must be carefully considered.In this study,a method of ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry(UHPLC-QTOF MS)was developed for the determination of PGA oligomers.The migration of oligomers in three distinct scenarios were investigated,i.e.packaging for frozen food,disposable containers with heat packaging for short-term storage,and containers for hot food and beverages.These scenarios were assessed in various food simulants,including acidic foods,non-acidic foods,and alcoholic beverages.The results showed that a total of 21 oligomers in PGA samples are identified,including 12 linear oligomers and 9 cyclic oligomers.Notably,the retention time of these oligomers increases with the increase of number of polymerization units.When PGA was employed as packaging for frozen foods,no oligomers are detected in food simulants containing 4%acetic acid,10%ethanol,or 50%ethanol.In contrast,a variety of linear and cyclic PGA oligomers are identified in the three food simulants when PGA was used for disposable containers with heat packaging and for hot food and beverages.This is particularly evident for linear oligomers GA5 to GA8 and cyclic oligomers GA6 to GA8.The potential mechanisms underlying the migration and formation of these oligomers can be explained that the non-crystalline regions of PGA are an amorphous state,where ester bonds are prone to gradual hydrolysis,facilitated by the diffusion of water molecules.This hydrolysis leads to the cleavage of chain segments,resulting in

关 键 词：超高效液相色谱-串联四极杆飞行时间质谱(UHPLC-QTOF MS) 聚乙醇酸 低聚物 迁移量 食品接触材料 

分 类 号：O657.63[理学—分析化学] TS206.4[理学—化学]