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食品安全国家标准 食品接触材料及制品 环氧氯丙烷的测定和迁移量的测定
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GB 31604.26-2016
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标准编号: GB 31604.26-2016 (GB31604.26-2016)
中文名称: 食品安全国家标准 食品接触材料及制品 环氧氯丙烷的测定和迁移量的测定
英文名称: Food contact materials -- Determination of epichlorohydrin in plastics -- High performance liquid chromatography
行业: 国家标准
中标分类: X09
字数估计: 18,136
发布日期: 2016-10-19
实施日期: 2017-04-19
旧标准 (被替代): SN/T 2897-2011; GB/T 23296.7-2009
标准依据: 国家卫生和计划生育委员会公告2016年第15号
GB 31604.26-2016: 食品安全国家标准 食品接触材料及制品 环氧氯丙烷的测定和迁移量的测定
GB 31604.26-2016 英文名称: Food contact materials -- Determination of epichlorohydrin in plastics -- High performance liquid chromatography
１ 范围
本标准规定了食品接触材料及制品（塑料、涂料、纸和纸板）中环氧氯丙烷的测定方法和迁移量的测
定方法。
本标准适用于食品接触材料及制品（塑料、涂料、纸和纸板）中环氧氯丙烷的测定方法和环氧氯丙烷
迁移量的测定方法，其中高效液相色谱法适用于食品接触材料及制品（塑料、涂料、纸制品）中环氧氯丙烷的测定，气相色谱-质谱法适用于食品接触材料及制品（塑料、涂料、纸和纸板）中环氧氯丙烷的迁移量的测定。
环氧氯丙烷的测定
２ 原理
试样中环氧氯丙烷经１，４-二氧六环提取后，提取液用微蒸馏装置进行蒸馏，馏出液中的环氧氯丙
烷经衍生后，其衍生物经过液相色谱分离，用荧光检测器测定环氧氯丙烷衍生物的含量，换算出试样中环氧氯丙烷的含量。采用外标法定量。
３ 试剂和材料
除非另有说明，本方法所用试剂均为分析纯，水为GB/T ６６８２规定的一级水。
３．１ 试剂
３．１．１ 乙腈（Ｃ２Ｈ３Ｎ）：色谱纯。
３．１．２ ９，１０-二甲氧基蒽-２-磺酸钠（Ｃ１６Ｈ１３ＮａＯ５Ｓ），即ＤＡＳ-Ｎａ。
３．１．３ １，４-二氧六环（Ｃ４Ｈ８Ｏ２）：纯度大于９９％，含水量应小于０．０１％。
３．１．４ 甲醇（ＣＨ４Ｏ）：色谱纯。
３．１．５ 强酸性阳离子交换树脂。
３．１．６ 氮气：纯度大于或等于９９．９％。
３．１．７ 冰块。
３．２ 试剂配制
３．２．１ 甲醇溶液（８０％，体积分数）
量取４００ｍＬ甲醇于５００ｍＬ容量瓶中，用水定容。
３．２．２ ９，１０-二甲氧基蒽-２-磺酸试剂（DAS试剂）
用２００ｍＬ甲醇溶液（８０％，体积分数）活化约５０ｇ预先处理好的强酸性阳离子交换树脂，然后用树脂填充内径为１ｃｍ 的玻璃柱，直至树脂高度约２０ｃｍ，备用。称取１００ｍｇ的ＤＡＳ-Ｎａ于预先盛有２０ｍＬ甲醇的烧杯中，加热溶解，将溶液分２次～３次全部过强酸性阳离子交换树脂。用甲醇洗脱，使流出液流速约为０．５ｍＬ／ｍｉｎ，收集ｐＨ为１～２时的洗脱液，直至ｐＨ开始上升。将所得洗脱液用氮吹仪吹干，制得ＤＡＳ试剂。应避光保存，保存期为一年。
称取２０ｍｇ（精确至０．１ｍｇ）ＤＡＳ试剂溶解于４ｍＬ乙腈中。临用现配，避光保存。
３．３ 标准品
环氧氯丙烷（Ｃ３Ｈ５ＣｌＯ，ＣＡＳ号：１０６-８９-８），纯度＞９９％，或经国家认证并授予标准物质证书的标准物质。
３．４ 标准溶液配制
称取１００ｍｇ（精确至０．１ｍｇ）环氧氯丙烷于１００ｍＬ容量瓶中，用１，４-二氧六环定容。溶液于-２０℃～２０℃避光密封储存，有效期为３个月。
准确移取２．０ｍＬ的环氧氯丙烷标准储备液（１ｍｇ／ｍＬ）至５０ｍＬ容量瓶中，用１，４-二氧六环定容。
３．４．３ 环氧氯丙烷的标准中间溶液
分别移取０．０ｍＬ、０．５ｍＬ、１．０ｍＬ、２．０ｍＬ、３．０ｍＬ、４．０ｍＬ、５．０ｍＬ的环氧氯丙烷标准使用液（４０μｇ／ｍＬ）于７个２５ｍＬ的容量瓶中，用１，４-二氧六环定容。标准中间液的浓度分别为０．０μｇ／ｍＬ、０．８μｇ／ｍＬ、１．６μｇ／ｍＬ、３．２μｇ／ｍＬ、４．８μｇ／ｍＬ、６．４μｇ／ｍＬ、８．０μｇ／ｍＬ。
３．４．４ 环氧氯丙烷标准工作溶液
分别移取１０．０ｍＬ１，４-二氧六环于７个样品瓶中，再分别准确加入１００μＬ环氧氯丙烷标准中间溶液，加入磁力搅拌棒，用隔垫和铝盖密封。并将样品瓶标记为Ａｂ。环氧氯丙烷标准工作溶液的浓度分别为：０μｇ／Ｌ、８μｇ／Ｌ、１６μｇ／Ｌ、３２μｇ／Ｌ、４８μｇ／Ｌ、６４μｇ／Ｌ、８０μｇ／Ｌ。
４ 仪器和设备
４．１ 高效液相色谱仪：配有２０μＬ定量环和荧光检测器。
４．２ 分析天平：感量分别为１ｍｇ和０．１ｍｇ。
４．３ 微蒸馏装置（如图Ａ．１所示）。
４．４ 氮吹仪。
４．５ 样品瓶：２０ｍＬ，配备铝盖和丁基橡胶隔垫或硅树脂橡胶隔垫，隔垫接触样品一面应涂有聚四氟乙烯。
注：如果没有合适样品瓶，可用顶空瓶代替。
４．６ 移液器：５０μＬ、１００μＬ。
４．７ 分析天平：感量０．１ｍｇ。
４．８ 微孔滤膜：０．２２μｍ。
注：使用的滤膜不应对环氧氯丙烷衍生物有吸附作用。
４．９ 容量瓶。
５ 分析步骤
５．１ 试样制备
测试与食品接触的塑料制品及纸和纸板样品时，样品裁剪成若干个面积为２ｄｍ２ 的小片，任取其中两片作平行试样。将２ｄｍ２ 的小片切割成大小１ｃｍ２ 的碎片，备用。对于涂层样品则轻轻刮下约０．２ｇ，备用。
５．２ 试样溶液的制备
５．２．１ 塑料及纸制品试样提取液的制备
将备用待测的塑料或纸制品称量０．５０ｇ（精确至０．１ｍｇ）后，浸入５０．０ｍＬ的１，４-二氧六环中，密封。在室温下提取６ｈ。移取１０．０ｍＬ提取液于２０ｍＬ样品瓶中，加入磁力搅拌棒，用隔垫和铝盖密封，并将顶空瓶标记为瓶Ａｓ。
５．２．２ 涂层提取液的制备
称取０．１５ｇ（精确至０．１ｍｇ）备用的涂层样品，浸入１５．０ｍＬ的１，４-二氧六环中，密封。在室温下提取６ｈ。移取１０．０ｍＬ提取液于样品瓶中，加入磁力搅拌棒用隔垫和铝盖密封，并将样品瓶标记为瓶Ａｓ。
注１：本标准规定了塑料制品、纸和纸板制品及涂层制品中环氧氯丙烷含量的测定方法。预期也可用于其他任何含有环氧氯丙烷的食品接触材料及制品。
注２：如果塑料包装试样或容器涂层较厚，应该提高温度或延长提取时间。整个提取过程应在密闭环境中进行以防止环氧氯丙烷逸出。
５．３ 空白溶液的制备
移取１０．０ｍＬ未与塑料、纸制品或涂层样品接触的１，４-二氧六环转入２０ｍＬ样品瓶中，加入磁力搅拌棒，用隔垫和铝盖密封，并将样品瓶标记为Ａ０。
５．４ １，４-二氧六环提取液的蒸馏
应用图Ａ．１的微蒸馏装置，将１，４-二氧六环提取液进行蒸馏，收集部分馏出液。图Ａ．１中瓶Ａ为５．２．１、５．２．２、５．３和３．４．４中的样品瓶，其中分别含有１０ｍＬ的试样提取溶液、空白溶液和标准工作溶液。
另取２０ｍＬ样品瓶，于体积为３ｍＬ处进行标记后用隔垫和铝盖密封。将密封后的样品瓶称量（精
确至０．１ｍｇ），并标记为瓶Ｂ。
如图Ａ．１所示，瓶Ａ和瓶Ｂ通过外层套有聚四氟乙烯的不锈钢管连接，钢管刺入瓶Ａ中的深度为
１ｃｍ～２ｃｍ，刺入瓶Ｂ中的深度３ｃｍ～４ｃｍ。为避免管口堵塞，应在样品瓶的瓶塞上预先刺一个小孔，使钢管可迅速刺入瓶中。同时，在瓶Ｂ的盖子上插入注射器针头以避免瓶中压力过大。
将瓶Ａ置于加热板上，将瓶Ｂ置于装有冰水混合物的烧杯中。加热瓶Ａ，使其中１，４-二氧六环提
取液沸腾，继续缓慢加热使瓶Ａ中的１，４-二氧六环提取液蒸馏至瓶Ｂ中，直至瓶Ｂ中馏出液面达到３ｍＬ标记处。将瓶Ａ从加热板上移开，移去瓶Ｂ中的注射器针头和不锈钢管。用滤纸仔细擦干瓶Ｂ。
将瓶Ｂ重新称量（精确至０．１ｍｇ），根据两次称量的差值和１，４-二氧六环的密度，计算馏出液的体积。
馏出液可于０℃～４℃密闭储存２周。
５．５ 环氧氯丙烷的衍生
打开含有馏出液的瓶Ｂ铝盖，加入５０μＬＤＡＳ-乙腈溶液（５ｍｇ／ｍＬ），用隔垫和铝盖密封。将样品瓶置于７５℃烘箱中１７ｈ±１ｈ。然后将衍生溶液冷却至室温，并用０．２２μｍ 的微孔滤膜过滤，滤液待测。
环氧氯丙烷的ＤＡＳ衍生物对光十分敏感，衍生应在避光条件下操作，衍生液可在室温下避光保存
２ｄ。
５．６ 仪器参考条件
仪器参考条件列出如下：
ａ） 色谱柱：Ｃ８，柱长２５０ｍｍ，内径为４．６ｍｍ，粒径为５μｍ，或相当者；ｂ） 流动相：乙腈和水，流动相梯度淋洗条件见表１；
ｃ） 进样量：２μＬ；ｄ） 流速：２ｍＬ／ｍｉｎ；
ｅ） 柱温：室温。
GB 31604.26-2016
GB
NATIONAL STANDARD OF THE
PEOPLE’S REPUBLIC OF CHINA
National Food Safety Standard - Food contact
materials and products - Determination of
epichlorohydrin and determination of migration
ISSUED ON. OCTOBER 19, 2016
IMPLEMENTED ON. APRIL 19, 2017
Issued by. National Health and Family Planning Commission of People's
Republic of China
Table of Contents
Foreword ... 3
1 Scope ... 4
Determination of epichlorohydrin ... 4
2 Principle... 4
3 Reagents and materials ... 4
4 Instruments and equipment ... 6
5 Analytical steps ... 7
6 Expression of the analytic result ... 10
7 Precision... 10
8 Others ... 10
Determination of migration of epichlorohydrin (gas chromatography-mass
spectrometry) ... 11
9 Principle... 11
10 Reagents and materials... 11
11 Instruments and equipment ... 14
12 Analytical steps ... 14
13 Expression of the analytic result ... 17
14 Precision ... 18
15 Others ... 18
Appendix A Micro distillation unit ... 19
Appendix B Liquid chromatogram of DAS derivatives of epichlorohydrin ... 20
Appendix C ... 23
Foreword
This standard replaces GB/T 23296.7-2009 "Food contact materials.
Determination of epichlorohydrin in plastics. High performance liquid
chromatography" and SN/T 2897-2011 “Food contact materials for export.
Metal materials. Determination of epichlorohydrin in coating. Gas
chromatography”.
In comparison with GB/T 23296.11-2009, the main differences of this
standard are as follows.
- Changed the name of the standard to "National Food Safety Standard -
Food contact materials and products - Determination of epichlorohydrin
and its migration";
- Added applicable scope;
- Revised the sample preparation method of coating;
- Added the determination method of the migration of epichlorohydrin in
food contacting materials and products.
National Food Safety Standard - Food contact
materials and products - Determination of
epichlorohydrin and determination of migration
1 Scope
This standard provides the determination method of epichlorohydrin in food
contact materials and products (plastics, paints, paper and cardboard) and
the determination method of migration.
This standard is applicable to the determination of epichlorohydrin in food
contact materials and products (plastics, paints, paper and cardboard) and
the determination of the migration of epichlorohydrin. The high performance
liquid chromatography (HPLC) is suitable for the determination of
epichlorohydrin in food contact materials and products (plastics, coatings,
paper products). The gas chromatography-mass spectrometry is suitable for
the determination of the migration of epichlorohydrin in food contact materials
and products (plastics, coatings, paper and cardboard).
Determination of epichlorohydrin
2 Principle
After extraction of epichlorohydrin from the sample by 1,4-dioxane, the extract
solution is distilled by a microdistillation unit. The epichlorohydrin in the
distilled liquid is derived and its derivatives are separated by liquid
chromatography. The content of epichlorohydrin derivatives is determined by
calculated. The external standard method is used for quantitative analysis.
3 Reagents and materials
Unless otherwise stated, the reagents used in this method shall be analytical
pure. The water shall be the primary water specified in GB/T 6682.
3.1 Reagents
3.1.1 Acetonitrile (C2H3N). chromatographic pure.
3.1.2 9,10-Sodium dimethoxanthrone-2-sulfonate (C16H13NaO5S), or
DAS-Na.
3.1.3 1,4-Dioxane (C4H8O2). purity≥ 99% and the water content< 0.01%.
3.1.5 Strong acid cation exchange resin.
3.1.6 Nitrogen. purity greater than or equal to 99.9%.
3.1.7 Ice.
3.2 Reagent preparation
3.2.1 Methanol solution (80%, volume fraction)
Take 400mL of methanol and put in 500ml volumetric bottle. Meter the volume
with water.
3.2.2 9,10-Sodium dimethoxanthrone-2-sulfonate reagent (DAS reagent)
Use 200 mL methanol solution (80%, volume fraction) to activate about 50g
column with inner diameter of 1cm to 20cm high. Put aside to be used. Weigh
100mg of DAS-Na add to a beaker containing 20ml methanol, heat to
dissolve. Pour the solution through the strong acid cation exchange resin.
Complete all the solutions in 2 times or 3 times. Elute with methanol and
make the flow rate of the effluent at about 0.5mL/min, collect the eluent at pH
1~2 until the pH begins to rise. Dry the obtained eluent with nitrogen blower to
get the DAS reagent. The DAS reagent should be kept away from light and
validity period is 1 year.
3.2.3 DAS-Acetonitrile solution (5mg/mL)
acetonitrile. Prepare when needed; keep away from light.
3.3 Standard product
Epichlorohydrin (C3H5ClO, CAS No.. 106-89-8). purity>99%, or a standard
substance certified by the State and granted the standard substance
certificate.
3.4 Standard solution preparation
3.4.1 Epichlorohydrin standard reserve solution (1mg/mL)
Take 10.0mL of 1,4-dioxane that is not in contact with plastic, paper or coating
samples and put it into a 20mL sample bottle, add magnetic stirring rod, seal
5.4 Distillation of 1,4- dioxane extract
Use the micro-distillation unit in figure A.1 to distill 1,4-dioxane extract and
collect the partial distillate. In figure A.1, bottle A are the sample bottles in
5.2.1, 5.2.2, 5.3 and 3.4.4, which contain 10mL sample extract solution, blank
solution and standard working solution respectively.
Take another 20mL sample bottles and mark at the volume of 3mL, then seal
with spacer and aluminum cap. Weigh the sealed sample bottle (precision to
0.1mg) and label as bottle B.
As shown in figure A.1, bottle A and bottle B are connected by a stainless
pierced into bottle A is 1cm~2cm and in bottle B is 3cm~4cm. To prevent the
inserted pipe from being blocked, prick a small hole on the bottle plug of the
sample bottle so that the steel pipe can quickly pierce into the bottle. Insert a
syringe needle on the bottle B's cover to avoid excessive pressure in the
bottle.
Place bottle A on a heating plate and put bottle B in a beaker containing a
mixture of ice water. Heat bottle A to boil the 1,4-dioxane extract, continue to
heat mildly and move the distilled1,4-dioxane extract to bottle B until the liquid
level reaches 3mL mark in bottle B. Remove bottle A from the heater and
bottle B carefully with filter paper. Reweigh bottle B (precision to 0.1mg).
Calculate the volume of distillate according to the difference between the two
weights and the density of 1,4-dioxane.
The distillate can be stored for 2 weeks at 0°C~ 4°C.
5.5 Derivatization of epichlorohydrin
Open the aluminum cover of bottle B containing distillate solution, add 50μL
of DAS-acetonitrile solution (5mg/mL), seal with spacer and aluminum cap.
Place the sample bottle in 75°C oven for 17h±1h, then cool the derivative
solution in room temperature and filter with 0.22μm microporous membrane.
The Das derivatives of epichlorohydrin are very sensitive to light. The
derivatization shall be performed under the condition away from light. The
derivatives can be stored in room temperature away from light for 2 days.
5.6 Instrument reference condition
Accurately weigh the standard material of epichlorohydrin 50 mg (precision to
0.1mg/g), transfer to 50mL volumetric flask with dichloromethane and dilute to
the scale. Seal to store at 0°C~ 4°C.
10.4.2 Epichlorohydrin standard intermediate for water-based, acidic
and alcohol food simulants (50mg/L)
into 100mL volumetric flask, dilute to scale with dichloromethane. Seal to
store at 0°C~ 4°C.
10.4.3 Epichlorohydrin standard intermediate for water-based, acidic
and alcohol food simulants (10mg/L)
Accurately move 1mL of epichlorohydrin standard reserve solution (1000mg/L)
into 100mL volumetric flask, dilute to scale with dichloromethane. Seal to
store at 0°C~ 4°C.
10.4.4 Epichlorohydrin standard intermediate for water-based, acidic
and alcohol food simulants (1mg/L)
into 50mL volumetric flask, dilute to scale with dichloromethane. Seal to store
at 0°C~ 4°C.
10.4.5 Epichlorohydrin standard working solution for water-based and
acidic food simulants
Add 2.5mL and 5.0mL of epichlorohydrin standard intermediate for
water-based, acidic and alcohol food simulants (1mg/L) and 10 mg/L, 2.5mL
and 5.0mL of epichlorohydrin standard intermediate for water-based, acidic
and alcohol food simulants (10mg/L) to 5 50mL volumetric flasks respectively.
Use the same food stimulants to dilute to scale. The concentrations of
0.1mg/L, 0.2mg/L, 0.5mg/L, 1.0mg/L respectively.
10.4.6 Epichlorohydrin standard intermediate for alcohol food simulants
Add 1mL, 2mL, 4mL, 10mL, 20mL of Epichlorohydrin standard intermediate
for water-based, acidic and alcohol food simulants (50mg/L) to 5 50mL
volumetric flasks respectively. Meter to scale with methanol. The
concentrations of this series of standard intermediates are 1.0mg/L, 2.0mg/L,
4.0mg/L, 10.0mg/L, 20.0mg/L.
10.4.7 Epichlorohydrin standard working solution for alcohol food
simulants
layer of dichloromethane extract liquid into a centrifuge tube and plug it.
According to the above steps, add again the dichloromethane 5mL accurately,
extract the simulant, and combine the extract liquid in the same centrifuge
tube. Record the volume of the extract liquid as V. Reserve to be used.
12.2.2 Preparation of alcohol and oil based food simulants
Accurately take 5mL of alcohol food simulants obtained from the migration
test or weigh 10g of the oil based simulants, place into 20mL headspace
bottles respectively, seal with spacer and aluminum cap, and set aside to be
used.
ethanol in the simulant solution to 10%. Operate as per 12.2.2.
12.2.3 Preparation of blank test solution
Treat the food simulants not in contact with food contact materials in
accordance with 12.2.
12.3 Dynamic headspace conditions
The options are set out in Appendix A.
Note. Refer to these conditions for the determination of epichlorohydrin in alcohol and
oil-based food simulants.
12.4 Reference conditions for Gas Chromatography-Mass Spectrometry
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