GB/T 22048-2022 English PDF (GB/T22048-2022)

GB/T 22048-2022: Determination of certain phthalate esters in toys and children products
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GB/T 22048-2022
GB
NATIONAL STANDARD OF THE
PEOPLE’S REPUBLIC OF CHINA
ICS 97.200.50
CCS Y 57
Replacing GB/T 22048-2015
Determination of certain phthalate esters in toys and
children’s products
(ISO 8124-6:2018, Safety of toys - Part 6: Certain phthalate esters in toys and
children’s products, MOD)
ISSUED ON: JULY 11, 2022
IMPLEMENTED ON: AUGUST 01, 2023
Issued by: State Administration for Market Regulation;
Standardization Administration of the People’s Republic of China.
Table of Contents
Foreword ... 3
1 Scope ... 6
2 Normative references ... 6
3 Terms and definitions ... 7
4 Principle ... 9
5 Reagents and materials ... 9
6 Instruments and equipment ... 10
7 Preparation of test portion ... 11
8 Analysis procedure ... 11
9 Calculation of results ... 17
10 Quality control ... 18
11 Precision ... 19
12 Test report ... 19
Annex A (normative) 7 phthalate esters tested in this document ... 20
Annex B (informative) Precision ... 21
Annex C (informative) Schematic diagrams of Soxhlet extractor and solvent extractor
... 25
Annex D (informative) Composite test ... 27
Annex E (normative) Ultrasonic extractor performance check ... 31
Annex F (informative) Determination examples of phthalate esters ... 34
Annex G (informative) Background and rationale ... 38
Bibliography ... 41
Determination of certain phthalate esters in toys and
children’s products
1 Scope
This document describes the determination methods for the plasticizer requirements in
5.3.7 of GB 6675.1-2014.
This document describes the determination methods for 7 kinds of phthalate esters
(according to the specifications in Table A.1) in toys and children’s products, i.e., di-
iso-butyl phthalate (DIBP), di-n-butyl phthalate (DBP), benzyl butyl phthalate (BBP),
bis-(2-ethylhexyl) phthalate (DEHP), di-n-octyl phthalate (DNOP), di-iso-nonyl
phthalate (DINP) and di-iso-decyl phthalate (DIDP).
This document is applicable to toys and children’s products containing polymers and
similar materials, textiles, coatings and liquid materials, and applicable to 5.3.7 of GB
6675.1-2014. This document has been validated for polyvinyl chloride (PVC),
polyurethane (PU) and some representative paint coatings, see Annex B. Other
materials for toys and children’s products can be determined with reference to this
document after validation.
The test of other phthalate esters can refer to this document after validation.
2 Normative references
The contents of the following documents constitute the essential provisions of this
document through normative references in the text. Among them, for dated references,
only the version corresponding to the date applies to this document; for undated
references, the latest version (including all amendments) applies to this document.
GB/T 454 Paper - Determination of bursting strength (GB/T 454-2020, ISO
2758:2014, MOD)
GB 6675.1-2014 Toys safety - Part 1: Basic code
GB 6675.2-2014 Safety of toys - Part 2: Mechanical and physical properties (ISO
8124-1:2000, MOD)
GB 6675.4-2014 Safety of toys - Part 4: Migration of certain elements (ISO 8124-
3:2010, MOD)
prepare a series of standard working solutions (prepare at least 5 standard working
solutions, of which the mass concentration of DIBP, DBP, BBP, DEHP, DNOP is 0.4
mg/L ~ 10 mg/L, and the mass concentration of DINP, DIDP is 2 mg/L ~ 50 mg/L),
each of the working solutions contains 10 mg/L of the internal standard.
The mass concentration of the internal standard can be adjusted according to the mass
concentration of the test portion, but the mass concentration of the internal standard in
the final sample solution (8.3.3) shall be consistent with the mass concentration of the
internal standard in the standard working solution. The standard working solution
containing the internal standard should be stored at a temperature of 0 °C ~ 8 °C, and
the validity period is 1 month.
6 Instruments and equipment
6.1 For normal laboratory glassware, phthalate esters are common contaminants, and
even a small amount can affect quantitative results. It is recommended to avoid the use
of any plastic equipment that may contaminate the analysis. Glassware and equipment
should be cleaned before use.
6.2 Gas chromatography/mass spectrometry (GC-MS): equipped with a quartz capillary
column and a mass spectrometer detector (EI source).
6.3 Soxhlet extractor: see Figure C.1. When necessary, with a cooling circulation device.
6.4 Solvent extractor (also known as fat extractor), see Figure C.2. When necessary,
with a cooling circulation device.
6.5 Extraction thimble: made of cellulose.
6.6 Cotton wool.
6.7 Analytical balance: an accuracy of 1 mg.
6.8 Concentration apparatus: such as a rotary evaporator, etc.
6.9 Solid phase extraction cartridge (SPE): 1 g silica gel/6 mL tubes, or equivalent.
6.10 Volumetric flasks: of 5 mL, 10 mL, 25 mL, 50 mL and 100 mL capacity.
6.11 Pipettes: of 0.2 mL, 0.5 mL, 1 mL, 2 mL, 5 mL and 10 mL capacity.
6.12 Organic phase microporous membrane filter: of pore size 0.45 μm, recommended
to use polytetrafluoroethylene (PTFE) microporous membrane filter.
6.13 Ultrasonic extractor: thermostatically controlled internally or externally, with the
effective ultrasonic power density ranging from 0.25 W/cm2 to 2.0 W/cm2.
Example:
One of the following methods can be selected for extraction according to the actual
situation.
8.2.1 Method A
Place the test portion in the extraction thimble (6.5) of a 250 mL Soxhlet extractor (6.3).
In order to prevent the test portion from floating, cotton wool (6.6) can be placed on the
upper layer of the extraction thimble.
Add 120 mL of dichloromethane (5.1) into a 250 mL round-bottom flask, extract for 6
h, and reflux at least 4 times per hour. If necessary, use a cooling circulation device for
cooling and refluxing.
The volume of the dichloromethane can be adjusted according to the extraction
equipment.
After cooling, use a suitable concentration apparatus (6.8) to concentrate until about 10
mL of the extract remains, and take care to prevent it from being completely evaporated
to dryness.
It is recommended to control the temperature of the water bath of a rotary evaporator at
40 °C ~ 50 °C, while maintaining the pressure at 30 kPa ~ 45 kPa.
Care shall be taken to control the temperature of reflux and concentration to prevent the
loss of phthalate esters.
8.2.2 Method B
Place the test portion in the extraction thimble (6.5) of a solvent extractor (6.4). In order
to prevent the test portion from floating, cotton wool (6.6) can be placed on the upper
layer of the extraction paper tube.
Add 80 mL of dichloromethane (5.1) into the extraction bottle, set a suitable
temperature (such as 80 °C), make the dichloromethane boil and reflux, extract for 1.5
h, then rinse for 1.5 h; if necessary, use a cooling circulation device for cooling and
refluxing. Finally, concentrate the extract to about 10 mL.
The volume of the dichloromethane can be adjusted according to the extraction
equipment.
Care shall be taken to control the temperature of reflux and concentration to prevent the
loss of phthalate esters.
8.2.3 Method C
8.2.3.1 Solid materials
Place the test portion in an airtight glass reaction vessel (6.15), and add 25 mL of
dichloromethane. Place the container in an ultrasonic extractor (6.13), the liquid level
in the ultrasonic tank shall be higher than the liquid level of the dichloromethane in the
reaction vessel, start at (60 ± 2) °C, and continue ultrasonication for 60 min. The
ultrasonic extractor performance check shall be carried out according to Annex E.
NOTE: If the material does not dissolve or swell in dichloromethane, Method A or Method B might
be preferable.
8.2.3.2 Liquid materials
Place the test portion in an airtight glass reaction vessel (6.15), and add 15 mL of
dichloromethane. Place the container in the ultrasonic extractor (6.13), the liquid level
in the ultrasonic water tank shall be higher than the liquid level of the dichloromethane
in the reaction vessel, start at (60 ± 2) °C, and continue ultrasonication for 60 min. The
ultrasonic extractor performance check shall be carried out according to Annex E.
8.3 Preparation of analytical solutions
8.3.1 General
If the extract obtained in 8.2.1, 8.2.2 or 8.2.3 is turbid, it can be centrifuged with a
centrifuge (6.16) at a centrifugal force of 5000 g before filtration. If necessary, the
extract can be purified with a solid phase extraction cartridge (6.9). Before purification,
pre-wash and activate with 10 mL of dichloromethane, discard the activation solution,
and then load the test portion, rinse with 3 mL of dichloromethane for 3 times and
collect the eluate.
The extract or the eluent, at room temperature, can be made up to the mark by 8.3.2
external standard method or 8.3.3 internal standard method according to the actual
situation.
8.3.2 Constant volume (external standard method)
8.3.2.1 Method A and Method B
Transfer the extract or the eluent into a 25 mL volumetric flask, make up to the mark
with dichloromethane, filter through the organic phase microporous membrane filter
(6.12), for GC-MS (6.2) analysis.
The final constant volume can be adjusted according to the mass and concentration of
the test portion. Care should be taken not to affect the limit of quantification (10.1).
8.3.2.2 Method C
8.3.2.2.1 Solid materials
f) Determination method: identification by full scan mode (full scan), quantification
by selected ion monitoring (SIM).
8.4.2 Qualitative analysis
Qualitative analysis is performed by comparing the retention time of target substance
and the relative abundance of characteristic ions in the test portion and the standard
working solution.
The following conditions can be used to determine whether the sample contains the
corresponding phthalate esters:
a) The deviation between the retention time of the target substance in the sample and
the retention time of the target substance in the standard working solution is
within ± 0.5 %;
b) The characteristic ions (see Table F.1) appear at the retention time of the target
substance in the standard working solution;
c) The relative abundance of the characteristic ions is consistent with the relative
abundance of the target substance in the standard working solution (if the relative
abundance > 50 %, a deviation of ± 10 % is allowed; if the relative abundance is
between 20 % ~ 50 %, a deviation of ± 15 % is allowed; if the relative abundance
is between 10 % ~ 20 %, a deviation of ± 20 % is allowed; if the relative
abundance is ≤ 10 %, a deviation of ± 50 % is allowed).
NOTE: Certain isomers of DINP or DIDP can interfere with the qualitative and quantitative
determination of DINP or DIDP. For example, dipropyl heptyl phthalate (DPHP, CAS No. 53306-
54-0) is one of the isomers of DIDP. It is difficult to separate DPHP from DIDP, but they can be
identified by features such as peak shape, retention time and abundance ratio.
8.4.3 Quantitative analysis
8.4.3.1 General
The laboratory can choose the external standard method or internal standard method for
quantification according to the actual situation. See G.4 for the selection conditions.
Select at least 5 standard working solutions (5.4 or 5.5.3) with different mass
concentrations for determination, and plot a standard curve with peak area versus mass
concentration. The linear correlation coefficient of the standard curve is not less than
0.995, and the corresponding value of phthalate easters in the sample solution shall be
within the linear range of the instrument. If necessary, it can be diluted with
dichloromethane.
Since GC-MS responds differently to DINP and DIDP standard substances with
different CAS numbers, the laboratory shall try to select a standard substance similar to
the test portion, and at the same time indicate the CAS numbers of DINP and DIDP in
the report, see Clause 12 f).
When integrating the peak area of isomers of DINP and DIDP, the baseline shall be
flattened before integration.
NOTE: Due to the existence of inseparable isomers, the peaks of DNOP, DINP and DIDP are
partially overlapped. By selecting m/z = 279 (DNOP), m/z = 293 (DINP) and m/z = 307 (DIDP) as
quantitation ions, it can minimize the mutual interference.
8.4.3.2 Calibration curve (external standard method)
Calculate the slope and ordinate intercept of the standard curve according to formula
(1):
where:
A - the peak area or sum of peak areas of the quantification ions of the certain
phthalate esters in the standard working solution;
a1 - the slope of the calibration curve, in liters per milligram (L/mg);
ρ - the mass concentration of the certain phthalate esters in the standard working
solution, in milligrams per liter (mg/L);
b1 - the ordinate intercept of the calibration curve.
8.4.3.3 Calibration curve (internal standard method)
Calculate the slope and ordinate intercept of the standard curve according to formula
(2):
where:
A - the peak area or sum of peak areas of the quantification ions of the certain
phthalate esters in the standard working solution;
AIS - the peak area of the quantification ions of the internal standard in the standard
working solution;
a2 - the slope of the calibration curve;
ρ - the mass concentration of the certain phthalate esters in the standard working
solution, in milligrams per liter (mg/L);
ws - the content of the certain phthalate esters in the test portion, %;
A - the peak area or sum of peak areas of the quantitation ions of the certain phthalate
esters in the test solution;
AIS - the peak area of the quantitation ion of the internal standard in the test solution;
b2 - the ordinate intercept of the calibration curve, which can be obtained from
formula (2);
ρIS - the mass concentration of the internal standard in the sample solution, in
milligrams per liter (mg/L);
a2 - the slope of the calibration curve, which can be obtained from formul...