Tiêu chuẩn iso 17881 1 2016

INTERNATIONAL
STANDARD

ISO
17881-1
First edition
2016-02-01

Textiles — Determination of certain
flame retardants —

Part 1:

Brominated flame retardants

Textiles  —  Détermination  de  certains  retardateurs  de  flamme  —
Partie  1:  Retardateurs  de  flamme  bromés

Reference number
ISO 17881-1:2016(E)
© ISO 2016


ISO 17881-1:2016(E)

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www.iso.org

ii

© ISO 2016 – All rights reserved


ISO 17881-1:2016(E)

Contents

Page

Foreword ........................................................................................................................................................................................................................................ iv

1
2
3
4
5

Scope ................................................................................................................................................................................................................................. 1
Principle ........................................................................................................................................................................................................................ 1
Reagents ........................................................................................................................................................................................................................ 1
Apparatus ..................................................................................................................................................................................................................... 2
Procedure ..................................................................................................................................................................................................................... 2

5.1
5.2
5.3

5 .4

Preparation of standard solutions ......................................................................................................................................... 2
5.1.1 Stock standard solution ............................................................................................................................................. 2
5.1.2 Internal standard solution....................................................................................................................................... 2
5.1.3 Working solution ............................................................................................................................................................. 3
Preparation of test specimen ...................................................................................................................................................... 3
Ultrasonic wave extraction ........................................................................................................................................................... 3
Flame retardants determination ............................................................................................................................................. 3

6
Calculation .................................................................................................................................................................................................................. 3
7
Test report................................................................................................................................................................................................................... 4
Annex A (informative) Test parameters by GC-MS ................................................................................................................................. 5
Annex B (informative) Round Robin test ......................................................................................................................................................... 7

© ISO 2016 – All rights reserved

iii


ISO 1 7881 -1 : 2 01 6(E)

Foreword

ISO (the International Organization for Standardization) is a worldwide federation of national standards

bodies (ISO member bodies). The work o f preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical

committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters o f
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
di fferent types o f ISO documents should be noted. This document was dra fted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
Attention is drawn to the possibility that some o f the elements o f this document may be the subject o f
patent rights. ISO shall not be held responsible for identi fying any or all such patent rights. Details o f
any patent rights identified during the development o f the document will be in the Introduction and/or

on the ISO list of patent declarations received (see www.iso.org/patents).

Any trade name used in this document is in formation given for the convenience o f users and does not

constitute an endorsement.

For an explanation on the meaning o f ISO specific terms and expressions related to con formity

assessment, as well as information about ISO’s adherence to the WTO principles in the Technical
Barriers to Trade (TBT) see the following URL: Foreword - Supplementary in formation
The committee responsible for this document is ISO/TC 38, Textiles.
ISO 17881 consists of the following parts, under the general title Textiles — Determination of certain
flame  retardants:
— Part  1:  Brominated  flame  retardants
— Part  2:  Phosphorus  flame  retardants

iv

© ISO 2016 – All rights reserved


INTERNATIONAL STANDARD

ISO 17881-1:2016(E)

Textiles — Determination o f certain flame retardants —

Part 1:

Brominated flame retardants
WARNING — This International Standard calls for the use o f substances and/or procedures
that may be injurious to health i f adequate precautions are not taken. It re fers only to technical
suitability and does not absolve the user from legal obligations relating to health and sa fety at
any stage. It has been assumed in the dra fting o f this International Standard that the execution
o f its provisions is entrusted to appropriately qualified and experienced people.

1 Scope
This part o f ISO 17881 specifies a test method for determining some brominated flame retardants in
textiles by gas chromatography – mass spectrometry (GC-MS).

The method is applicable to all kinds of textile products.
2 Principle

The flame retardants are extracted from textile specimen by ultrasonic generator with toluene. The flame
retardants in the specimen are identified by GC-MS and quantified by using internal standard method.

3 Reagents
Unless otherwise specified, use only reagents o f recognized analytical grade.

, CAS no. 2052-07-5.

3 .1

Monobromobiphenyl (MonoBB)

3 .2

Dibromobiphenyl (DiBB)

3 .3

Tribromobiphenyl (TriBB)

3 .4

Tetrabromobiphenyl (TetraBB)

3 .5

Pentabromo-1,1’-biphenyl (PentaBB)

3 .6

Hexabromobiphenyl (HexaBB)

3 .7

Heptabromo-1,1’-biphenyl (HeptaBB)

3 .8

Octabromobiphenyl (OctaBB)

3 .9

Nonabromobiphenyl (NonaBB)

, CAS no. 57422-77-2.
, CAS no. 59080-34-1.
, CAS no. 60044-24-8.
, CAS no. 59080-39-6.

, CAS no. 60044-26-0.

, CAS no. 88700-06-5.

, CAS no. 67889-00-3.

3 .10 Decabromobiphenyl (DecaBB)

, CAS no. 69278-62-2.

, CAS no. 13654-09-6.

3 .11 Tetrabromodiphenylether (TetraBDE)

© ISO 2016 – All rights reserved

, CAS no. 5436-43-1.
1


ISO 17881-1:2 016(E)

, CAS no.32534-81-9.

3 .1 2

Pentabromodiphenylether (PentaBDE)

3 .1 3

Hexabromodiphenylether (HexaBDE)

3 .1 4

Heptabromodiphenylether (HeptaBDE)

3 .1 5

Octabromodiphenylether (OctaBDE)

3 .1 6

Decabromodiphenylether (DecaBDE)

3 .1 7

Hexabromocyclododecane (HBCDD)

3 .1 8

Decachlorobiphenyl

3 .1 9

Toluene

, CAS no. 207122-15-4.

, CAS no. 207122-16-5.

, CAS no. 337513-72-1.
, CAS no. 1163-19-5.

, CAS no. 25637-99-4.

, CAS no.2051-24-3, internal standard (IS).

.

NOTE
Since brominated flame retardants have many isomers, this method might not cover all o f them.
Determination o f the isomers o f flame retardants in Clause 3 can refer to this method according to the principle.
4

Apparatus

4.1

Gas chromatography – mass spectrometry (GC-MS)

4.2

Ultrasonic generator

4.3

Evaporator device

4.4

Brown glass vial

4.5

Flask

4.6

Filtration membrane

4.7

Balance

5

.

, with a frequency from 35 kHz to 45 kHz.

, with water bath at 50 °C.

, 40 ml with tight closure.

, 100 ml.
, 0,45 µm.

, an accuracy o f 0,1 mg.

Procedure

5 .1

5 .1 .1

Preparation o f standard solutions

Stock standard solution

Prepare 1 000 µg/ml o f stock standard solutions with individual flame retardant (3.1
internal standard (3.18) in toluene (3.19).

to 3.17) and

Some commercial re ference material solutions may be available in a di fferent solvent.
5 .1 .2

Internal standard solution

Prepare 10 µg/ml standard solution o f decachlorobiphenyl in toluene.

2

© ISO 2016 – All rights reserved


ISO 17881-1:2 016(E)

5 .1 .3

Working solution

P rep a re an ad m i xture worki ng s olution o f 17 fl ame re ta rda nts i n i nterna l s ta ndard s olution (

5.1.2) and

d i lute it to a s erie s o f s u itable concentration s dep end i ng on te s t ne e d s . S ele c t at le as t five d i lution s o f
the c a l ibration s e ts to cre ate c a l ibration c u r ve and p er form G C-M S ana lys i s .

Preparation o f test specimen

5 .2

Prepare a representative test specimen of the sample. Cut it into small pieces and weigh (1,00 ± 0,01) g
of the pieces with a balance ( ).
4.7

5 .3

Ultrasonic wave extraction

Put the pieces in a vial with tight closure ( ) and add 20 ml of toluene. Place the vial in an ultrasonic
generator ( ) and extract the pieces for 30 min at room temperature. Filter and transfer the
). Add 10 ml of toluene to the residue in the vial and place the vial in
the ultrasonic generator to extract the residue for 15 min at room temperature. Filter and merge the
).
). Add 2 ml of internal standard solution
f
(5.1.2
4.4

4. 2

e x trac t i nto 1 0 0 m l fl a s k (4 . 5

e x trac t i nto the fl a s k (4 . 5

E vap orate the e xtrac t to ne a r d r yne s s b y evap orator device (4. 3

) to d i s s olve the re s idue a nd then fi lter b y fi ltration membrane (4. 6) . T he fi ltrate i s re ady

or

de term i nation o f flame re tardants .

5 .4

Flame retardants determination

5.3
given in Annex A as an example. Run a blank to control contamination.
D e term i ne the flame re tardants i n the s olution (

) b y G C-M S (4.1) . T he te s t p ara me ters b y G C -M S are

When the flame re ta rdants level i s ver y low, it i s ne ce s s ar y to i ncre as e the ma s s o f the pie ce s i n order to

reach at least three times the detection limit.

When the flame re ta rdant level i s b eyond the l i ne ar de te c tor re s p on s e range o f the e qu ipment, it i s
ne ce s s ar y to d i lute the s p e ci men l iquid prop erly.

6

Calculation

Qua nti fy the concentration o f e ach fla me re tardant by u s i ng the c a l ibration c u r ve . T he content o f e ach
flame re tardant i s e xpre s s e d b y the mas s ratio o f flame re tardant to te s t s p e c i men, i n μg/g. C a lc u late
the re s u lt b y u s i ng Formu l a (1) .

Xi =

(

Ci − C0 ) × V
m

(1)

where
Xi

i s the content o f the fl ame re tardant, i, i n the te xti le s p e c i men, i n μg/g;

Ci

i s the concentration o f the fl ame re ta rd ant, i, i n the s p e c i men s olution, i n μg/m l;

0

C

i s the concentration o f the fl ame re ta rd ant, i, i n the b lan k s olution, i n μg/m l;

V

i s the fi na l volu me o f the s p e ci men s olution, i n m l;

m

is the mass of the test specimen, in g.

© ISO 2016 – All rights reserved

3


ISO 17881-1:2016(E)

7 Test report

The test report shall include the following information:
a)

a re ference to th i s p a r t o f I S O 178 81 , i . e . I S O 178 81-1 : 2 016;

b)

a l l de tai l s ne ce s s ar y

c)

the content o f e ach flame re tardant;

d)

any devi ation

4

from

for

identi fic ation o f the s a mple te s te d;

the pro ce du re s p e c i fie d .

© ISO 2016 – All rights reserved


ISO 17881-1:2016(E)

Annex A

(informative)
Test parameters by GC-MS

A.1

Instrument parameters

As the instrumental equipment o f the laboratories may vary, no generally applicable parameters can be
provided for chromatographic analyses. The following parameters have been found success fully.

a)

VF-5ht, length 15 m, inside diameter 0,25 mm,
film thickness 0,1 μm or equivalent;

Capillary column:

b) Temperature programme:
c) Injector temperature:
d) Transfer line temperature:
e) Carrier gas:

100 °C for 2 min, 100 °C to 310 °C (20 °C/min), 310 °C for 5 min;
280 °C;
300 °C;
Helium with a purity o f no less than 99,999 % delivered at
1,5 ml/min;

f) Ionization mode:
g) Ionization energy:
h) Detection mode:
i) Injector system:

Splitless, split at 1 min;

j)

1 μl.

EI;
70 eV;
Selected ion monitor detection;

Injector volume:

A.2

Typical ions and detection limit

Typical ions and detection limit for flame retardants are shown in Table A.1.
Table A.1 — Typical ions and detection limit

No.
1
2
3

4

5
6
7
8
9

Flame retardant
Monobromobiphenyl (MonoBB)
Dibromobiphenyl (DiBB)
Tribromobiphenyl (TriBB)

Tetrabromobiphenyl (TetraBB)
Pentabromo-1,1’-biphenyl (PentaBB)
Hexabromobiphenyl (HexaBB)
Heptabromo-1,1’-biphenyl (HeptaBB)
Octabromobiphenyl (OctaBB)
Nonabromobiphenyl (NonaBB)

© ISO 2016 – All rights reserved

Typical ions/amu

Target ion
152
152
230
310
388
468
546
544

705

Target ion

234, 232, 152

312, 310, 152

392, 390, 230

470, 310, 308
550, 390, 388
628, 468, 466
705, 546, 544
785, 546, 544
864, 705, 703

Detection limit
(μg/g)

5
5
5
5
5
5
10
10
10

5


ISO 1 7881 -1 : 2 01 6(E)

Table A.1

No.
10
11

12
13
14

15
16
17
18

6

Flame retardant
D e c abro mo b ip henyl ( D e c a B B )
Te trabromo d ip henyle ther ( Te tra B D E )

(continued)
Typic a l ion s/a mu

Target ion
783
326

Target ion

9 4 4, 78 3 , 78 1
48 8, 486, 32 6

Pentab ro mo d iphenyle ther ( Penta B D E )

40 4

5 6 4, 4 0 6 , 4 0 4

H e xab romo d ip henyle ther ( H e xa B D E )

484

6 43 , 4 8 4, 4 8 2

H ep tabromo d ip henyle ther(H ep ta B D E )

562

7 2 2 , 5 62 , 45 6

O c tab romo d ip henyle ther (O c ta B D E )

6 42

8 01 , 6 42 , 6 3 9

D e c ab ro mo d ip henyle ther ( D e c aB D E )

79 9

9 5 9, 79 9, 79 7

H e xab romo c yclo do de c a ne ( H B C D D)
D e c ach loro bip henyl (I S )

157

49 8

3 19, 2 3 9, 1 5 7
49 8 , 42 8 , 2 14

Detection limit
(μg/g)

10
5
5
5
5
5
10
10
—

© ISO 2016 – All rights reserved


ISO 17881-1:2016(E)

Annex B

(informative)
Round Robin test

T he Rou nd Robi n te s t wa s c arrie d out b y five tex ti le lab oratorie s i n C h i na .

A total of nine samples were prepared, three from cotton woven fabrics (no.1 to 3), three from
p olye s ter woven

fabrics

(no .4 to 6 ) , and th re e

from

5 0 co tton/5 0 p olye s ter woven

fabrics

(no .7 to 9)

e ach conta i n i ng s i x fla me re ta rda nts , i . e . D i B B , PentaB B , D e c aB B , PentaB DE , D e c aB DE , a nd H B C DD .

The three samples from each fabric were at three concentration levels of 50mg/kg, 200 mg/kg, and
5 0 0 mg/ kg. T h re e te s t s p e c i men s

from

e ach s ample were te s te d i n e ach l ab orator y.

The results of the Round Robin test are shown in Table B.1.
Table B .1 — Results o f the Round Robin tes t

Sample

no.

1

2

3

4

E xp ected

Substance

DiBB
PentaBB
DecaBB
PentaBDE
DecaBDE
HBCDD
DiBB
PentaBB
DecaBB
PentaBDE
DecaBDE
HBCDD
DiBB
PentaBB
DecaBB
PentaBDE

DecaBDE
HBCDD
DiBB
PentaBB
DecaBB
PentaBDE
DecaBDE
HBCDD

value

(mg/ kg)

50
50
50
50
50
50
200
200
200
200
200
200
500
500
500
500
500

500
50
50
50
50
50
50

© ISO 2016 – All rights reserved

Mean

Recovery

(mg/ kg)

(%)

49, 62

9 9, 2 4

45 , 0 0

90,00

4 4,76

8 9, 5 2

42 , 5 2

85,03

46, 2 3

9 2 ,4 6

46, 5 6

9 3 ,1 2

19 9, 3 7

9 9, 6 8

19 8 , 8 4

9 9, 42

19 1 , 3 9

9 5 ,70

1 8 9,9 6

9 4,9 8

183,85

9 1 ,9 3

Repeatability

Sr (mg/ kg)

2,08
1 ,9 7

1,63

1 ,46

1,82
2,78
6,71
6,77
6,28
8,26
9, 51

6,16

19 2 , 0 5

96,03

49 1 ,4 8

98,30

1 3 ,9 9

4 8 2 ,4 6

9 6 ,49

2 1 ,19

478 ,75

9 5 ,75

479, 2 3

95 , 85

4 8 0 ,4 0

96,08

475 , 2 8

95 ,06

4 6 ,14

92 , 2 8

4 4,9 0

8 9,7 9

47, 0 7

20,72
9,47

CVr (%)
4, 2 0
4, 3 7
3 ,64

5,72
6,16

11,52
1 3 , 69

3 ,9 4

7,9 7

17, 2 4

5 ,9 6

1 ,79

3 ,42

3,36
3 ,41

3,28
4, 3 5

5,17
3,21
2,85
4, 3 9
4, 3 3
1 ,9 8

9 4,14

2 ,14

4, 5 5

41 ,70

8 3 ,4 0

1 ,43

3 ,43

46, 3 5

9 2 ,70

87,68

CVR (%)

14, 3 0

3,88

43 , 8 4

SR (mg/kg)

6 ,4 01

18,65
35,11
2,38
1,30
2,00
2,23

Reproducibility

7, 3 9

5,17
2 ,9 0

4, 3 1

5,08

7,57

14, 0 4
1 2 ,49

10,35

1 5 , 69

20,68
7,70
4 6 ,4 4

17,82
3,85
7, 0 4

6,28
5 ,41

8,26
11,25
4, 01
9,45

12,12

27,11

2,51
5,66

19,74

4,1 2

23 , 59

4,91

28,18
3,50
6,30
7,42

7,82
8,85
6, 59

5 ,9 3
7, 59
14, 0 3

15,77
18,76
19,1 1
15,0 4

7


ISO 17881-1:2016(E)

Table B .1

Sample
no .

5

6

7

8

9

8

E xp ected

Substance

DiBB
PentaBB
DecaBB

PentaBDE
DecaBDE
HBCDD
DiBB
PentaBB
DecaBB
PentaBDE
DecaBDE
HBCDD
DiBB
PentaBB
DecaBB
PentaBDE
DecaBDE
HBCDD
DiBB
PentaBB
DecaBB
PentaBDE
DecaBDE
HBCDD
DiBB
PentaBB
DecaBB
PentaBDE
DecaBDE
HBCDD

value

(mg/ kg)

200
200
200
200
200
200
500
500
500
500
500
500
50
50
50
50
50
50
200
200
200
200
200
200
500
500
500
500

500
500

(continued)

Repeatability

Repro ducibi lity

Mean

Recovery

(mg/ kg)

(%)

Sr (mg/ kg)

CVr (%)

SR (mg/ kg)

19 2 , 47

96,24

7,9 6

4 , 14

10 , 6 4

19 1 , 0 8

95 , 5 4

10,80
6,57
7,65

5,65
5,03
3,63

11,75
16,27
15,06
15,05
12,76

3 , 69

3 0 ,69

185,75

92 , 87

1 8 9, 2 8

9 4, 6 4

1 8 7,9 9

9 4, 0 0

180,58

90,29

4 8 0 ,9 3

9 6 , 19

483 , 82

9 6 , 76

47 9 , 5 4

9 5 ,9 1

47 3 , 41

9 4, 6 8

468 , 3 9

93 ,68

485 , 21

9 7, 0 4

47, 14

9 4, 2 9

4 4 , 67

8 9, 3 4

45 , 0 3

90,06

40, 33

80,66

45 , 43

90,86

42 , 5 2

85 ,0 4

1 8 9,4 0

9 4 , 70

202,38

1 0 1 ,19

1 8 9, 6 3

9 4, 8 2

1 8 9, 0 5

9 4, 5 3

19 1 ,9 4

9 5 ,9 7

17 9,1 8

8 9, 59

47 5 ,9 7

9 5 ,19

49 4,4 6

98,89

503,78

100,76

47 7,9 3

95 , 59

47 9 , 8 7

9 5 ,9 7

4 8 9, 3 3

9 7, 8 7

9,4 6

6,55
17,75
13,65

3,54

4, 0 4

7,21

2,82

2,70
1,52

16, 59

3,54

1 2 ,9 4

13,84

25,24

2 8 , 69

18,11
17,67

21,12
1,52

3,23

1 ,7 9

4, 01

6 ,9 9

2,73

2,06
2,70
2,21
7,37

6,05
5,11

3,06

5,89

8,12
3 ,9 9

4, 3 5

5 ,9 4

5 ,19

3 ,89

2 ,9 1

4, 2 8

2,11
3,68

4, 3 1

8 ,9 3

5,61

7,9 6

8,00
7,07
6,38
2,86
5,26
6,06
3,87
3 ,64

9,1 5

15,65
6 ,79

22,15
12 ,34

10 , 69

10,50
12,36
5,80

15,31
7,78
15,56

5,55
6,11
3,06
8,10

6,57
2,27
3,22
2,57

19,7 3

4,1 1

35,29

4, 2 3

13 ,0 4

20,70

5,53
6,15
8,76

4, 5 4

7,07
7,65
31,27
11,23
16,22
12,26

4, 2 7

CVR (%)

41 , 19

23,03
2 4 ,9 5

8 ,9 5

4, 0 5

8 , 69

8,65
4, 6 6

4 ,9 5

1,87

7,35
2,67

© ISO 2016 – All rights reserved



ISO 1 7881 -1 : 2 01 6(E)

ICS  59.080.01

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© ISO 2016 – All rights reserved