EN ISO TS 16179-2012 en Footwear - Critical substances potentially present in footwear and footwear components - Determination of organotin compounds in footwear materials《鞋类 鞋类与其组.pdf

1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationFootwear Critical substances potentially present in footwear and footwear components Determination of organotin compounds in footwear materialsPD CEN/ISO TS 16179:2012National fo

2、rewordThis Published Document is the UK implementation of CEN/ISO TS 16179:2012.The UK participation in its preparation was entrusted to Technical Committee TCI/69, Footwear, leather and coated fabrics.A list of organizations represented on this committee can be obtained on request to its secretary.

3、This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2012Published by BSI Standards Limited 2012 ISBN 978 0 580 74886 8 ICS 61.060Compliance with a British Standard cannot confer

4、immunity from legal obligations.This Published Document was published under the authority of the Standards Policy and Strategy Committee on 31 August 2012.Amendments issued since publicationDate Text affectedPUBLISHED DOCUMENTPD CEN/ISO TS 16179:2012TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TEC

5、HNISCHE SPEZIFIKATION CEN ISO/TS 16179 August 2012 ICS 61.060 English Version Footwear - Critical substances potentially present in footwear and footwear components - Determination of organotin compounds in footwear materials (ISO/TS 16179:2012) Chaussures - Substances critiques potentiellement prse

6、ntes dans les chaussures et les composants de chaussures - Dtermination des composs organostanniques dans les matriaux de chaussures (ISO/TS 16179:2012) Schuhe - Mglicherweise in Schuhen und Schuhbestandteilen vorhandene kritische Substanzen - Bestimmung zinnorganischer Verbindungen in Schuhwerkstof

7、fen (ISO/TS 16179:2012) This Technical Specification (CEN/TS) was approved by CEN on 6 August 2012 for provisional application. The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to submit their comments, particularly on th

8、e question whether the CEN/TS can be converted into a European Standard. CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at national level in an appropriate form. It is permissible to keep conflicting national s

9、tandards in force (in parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic

10、of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISAT

11、ION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN ISO/TS 16179:2012: EPD CEN/ISO TS 16179:2012CEN ISO/TS 16179:2012 (E) 2 Contents Page For

12、eword 3PD CEN/ISO TS 16179:2012CEN ISO/TS 16179:2012 (E) 3 Foreword This document (CEN ISO/TS 16179:2012) has been prepared by Technical Committee CEN/TC 309 “Footwear“, the secretariat of which is held by AENOR, in collaboration with Technical Committee ISO/TC 216 “Footwear“. Attention is drawn to

13、the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following cou

14、ntries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norw

15、ay, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. PD CEN/ISO TS 16179:2012ISO/TS 16179:2012(E) ISO 2012 All rights reserved iiiContents Page1 Scope 12 Normative references . 13 Principle . 14 Reagents 15 Apparatus and materials . 26 Prepara

16、tion of the test piece 37 Procedure 37.1 Preparation of the sodium tetraethylborate solution 37.2 Preparation of standard solutions 47.3 Preparation of the tropolone solution 57.4 Preparation of the buffer solution . 57.5 Calibration . 57.6 Sample preparation . 67.7 Preparation of the blank solution

17、 . 67.8 Gas chromatography 67.9 Quantification . 77.10 Detection limit and quantification limit 88 Test report . 8Annex A (informative) Suggested gas chromatography-mass spectrometry (GC-MS) conditions for organotin analysis .10Annex B (informative) Reliability of the method 11Bibliography .12PD CEN

18、/ISO TS 16179:2012TECHNICAL SPECIFICATION ISO/TS 16179:2012(E)Footwear Critical substances potentially present in footwear and footwear components Determination of organotin compounds in footwear materials1 ScopeThis Technical Specification specifies a test method for determining the presence of org

19、anotin compounds. This test method is applicable to all types of footwear materials.NOTE ISO/TR 16178 defines which materials are concerned by this determination.2 Normative referencesISO 3696, Water for analytical laboratory use Specification and test methods3 PrincipleThe organotin substances are

20、extracted from the footwear material with a methanol-ethanol mixture, in a medium-strength acidic condition, using tropolone as a complexant agent.The polar and high-boiling organotin is then converted to the corresponding volatile tetra-alkyl derivative, by reaction with sodium tetraethylborate, Na

21、B(Et)4. Finally, it is detected by a gas chromatograph fitted with a mass selective detector (GC-MS).Table 1 indicates the list of target compounds which can be analysed with this Technical Specification.Table 1 List of target compounds which can be analysed with this Technical SpecificationType of

22、compound Compound CASaMonosubstitutedn-butyltin trichloride 1118- 46-3n-octyltin trichloride 3091-25-6DisubstitutedDi-n-butyltin dichloride 683-18-1Di-n-octyltin dichloride 3542-36-7TrisubstitutedTri-n-butyltin chloride 1461-22-9Triphenyltin chloride (or fentin chloride) 639-58-7Tricyclohexyltin chl

23、oride 3091-32-5Tetrasubstituted Tetra-n-butyltin 1461-25-2aChemical Abstract Service.4 ReagentsUnless otherwise specified, use only reagents of recognized analytical grade.4.1 Water, grade 3 according to ISO 3696.4.2 Ethanol, GPR grade or industrial methylated spirit (IMS), CAS number: 64-17-5.4.3 G

24、lacial acetic acid, CAS number: 64-19-7. ISO 2012 All rights reserved 1PD CEN/ISO TS 16179:2012ISO/TS 16179:2012(E)4.4 Sodium tetraethylborate, CAS number: 15523-24-7.4.5 Tetrahydrofuran (THF), stabilized, CAS number: 109-99-9.4.6 n-heptyltin trichloride, CAS number: 59344-47-7 (internal standard).4

25、.7 Di-n-heptyltin dichloride, CAS number: 74340-12-8 (internal standard).4.8 Tri-n-propyltin monochloride, CAS number: 2279-76-7 (internal standard).4.9 Tetra-n-propyltin, CAS number: 2176-98-9 (internal standard).4.10 Isooctane, CAS number: 540-84-1.4.11 Inert gas, e.g. nitrogen, helium or argon.4.

26、12 Tropolone (2-hydroxy-2,4,6-cycloheptatrien-1-one), of laboratory grade, CAS number: 533-75-5.4.13 Methanol, of analytical grade, CAS number: 67-56-1.4.14 Sodium acetate, CAS number: 127-09-3.4.15 Organotin compounds listed in Table 1.5 Apparatus and materials5.1 GC-MS gas chromatograph fitted wit

27、h a mass selective detector (MS).5.2 Analytical balance, capable of measuring mass to an accuracy of 0,1 mg.5.3 Glove bag, box or isolation chamber with built-in gloves that enables work to be carried out in a totally isolated and controlled environment and has side and front openings and means of s

28、ealing the openings, such as tape.5.4 Sample tubes of polypropylene, with screw tops and a volume of 50 ml.5.5 Micropipettes, 10 l to 500 l range, with disposable tips.5.6 Pipette, 1 ml to 10 ml capacity.5.7 Calibrated pH-meter with a glass combination electrode and range of 0 to 14.5.8 Volumetric f

29、lasks of 10 ml, 25 ml and 100 ml.5.9 Ultrasonic bath with adjustable temperature.5.10 Disposable glass Pasteur pipettes.5.11 Glass beaker.5.12 Centrifuge.2 ISO 2012 All rights reservedPD CEN/ISO TS 16179:2012ISO/TS 16179:2012(E)5.13 Mechanical shaker, adjusted to a minimum frequency of 50 min1.6 Pre

30、paration of the test pieceThe test piece consists of a single material taken from the footwear, such as leather, textile, polymer, coated material or other. The preparation of the sample should involve the removal of the individual materials from the footwear and the preparation of a test piece, whi

31、ch results in particles with a maximum diameter of 4 mm or less.7 ProcedureSAFETY PRECAUTIONS Sodium tetraethylborate solution shall be prepared in an inert atmosphere, as this material is air-sensitive and can spontaneously combust in the presence of air. The solution should be prepared in an empty

32、 fume cupboard, using the method provided, in order to minimize fire risks. Organotins are both toxic and known endocrine system disrupters; therefore, they should be treated with utmost care.NOTE All the chemicals that are stored below room temperature should be allowed to reach room temperature be

33、fore an aliquot is taken.7.1 Preparation of the sodium tetraethylborate solution7.1.1 Preparation shall be carried out in an inert environment.7.1.2 Place the analytical balance inside the inert environment, taking the power cord through one of the small side openings, using tape to seal the opening

34、 around the cord.7.1.3 Place the following items in the inert environment: a small beaker (5.11); a sealed bottle of sodium tetraethylborate (4.4); a large spatula, a small spatula and a small beaker containing THF (4.5); a disposable pipette (5.10).7.1.4 Using an inert gas supply (4.11) connected t

35、hrough the side of the inert environment, fill the bag with gas, allowing mixed air and inert gases to be expelled through the front opening for several minutes. This will ensure that any remaining oxygen is of sufficiently low concentration not to support combustion.7.1.5 Seal the front opening of

36、the inert environment and turn off the inert gas supply.7.1.6 Using the gloves in the side of the bag, weigh out 2,0 g sodium tetraethylborate (4.4) into the beaker (5.11), then add sufficient THF (4,5) to dissolve the borate (less than 10 ml).7.1.7 Re-seal the top of the sodium tetraethylborate bot

37、tle.7.1.8 Open the front of the bag and remove all of the items, leaving them inside the fume cupboard for later cleaning.7.1.9 Transfer the sodium tetraethylborate solution from the beaker (5.11) into a 10 ml volumetric flask (5.8) and make up to the mark with THF (4.5). Store the reagent for a max

38、imum of three months in a fridge, when not in use, to minimize evaporation of the solvent.NOTE Pre-weighed tetraethylborate or commercial solutions are available on the market. ISO 2012 All rights reserved 3PD CEN/ISO TS 16179:2012ISO/TS 16179:2012(E)7.2 Preparation of standard solutions7.2.1 Genera

39、lThe organotin compounds are available on the market under their chloride forms, but the concentration for the calibration curve and the result are expressed in mg/kg of organotin cations.EXAMPLE 1 With the dibutyltin dichloride, Bu2SnCl2(dibutyltin dichloride) is the chloride form and Bu2Sn2+is the

40、 cation form.Table 2 gives the amount of organotin chloride and the weighting factor for recalculation of organotin cations (for 100 % purity of the chloride form).Table 2 Amount of organotin chloride and weighting factor for recalculation of organotin cationsCompound Weighting factorAmount of organ

41、otin chloride required to have a solution of 1 000 mg/l of organotin cation (in a 100 ml flask) mgTarget compoundsn-butyltin trichloride 0,623 160,5n-octyltin trichloride 0,686 145,8Di-n-butyltin dichloride 0,767 130,4Di-n-octyltin dichloride 0,830 120,5Tri-n-butyltin chloride 0,891 112,2Triphenylti

42、n chloride 0,908 110,1Tricyclohexyltin chloride 0,912 109,6Tetra-n-butyltin 1,000 100,0Internal standardsn-heptyltin trichloride 0,672 148,8di-n-heptyltin dichloride 0,817 122,4tri-n-propyltin monochloride 0,875 114,3tetra-n-propyltin 1,000 100,0EXAMPLE 2 If you weigh 160,5 mg of monobutyltin trichl

43、oride (BuSnCl3), you have a solution of 1 605 mg/l of monobutyltin trichloride, which corresponds to a concentration of: 1 605 0,623 = 1 000 mg/l of monobutyltin cation (BuSn3+). EXAMPLE 3 If you weigh 110,4 mg of dioctyltin dichloride (C8H17)2SnCl2), you have a solution of 1 104 mg/l of dioctyltin

44、dichloride, which corresponds to a concentration of: 1 104 0,830 = 916 mg/l of dioctyltin cation (C8H17)2Sn2+.The concentration of organotin cation is usually calculated using Formula (1):CSn =CCl WF (1)whereCSnis the concentration of organotin cation (mg/l);CClis the concentration of organotin chlo

45、ride (mg/l);WF is the weighting factor.4 ISO 2012 All rights reservedPD CEN/ISO TS 16179:2012ISO/TS 16179:2012(E)7.2.2 Internal standards stock solution (1 000 mg/l of organotin cation)Use the analytical balance (5.2) to weigh the appropriate amount of tripropyltin hydrochloride (4.8), monoheptyltin

46、 trichloride (4.6), diheptyltin dichloride (4.7) and tetrapropyltin (4.9). Dissolve them together in methanol (4.13) in a single volumetric flask (5.8) of at least 100 ml to obtain the concentration of 1 000 mg/l for each substance.Store the standard solution for a maximum of one year in a fridge, w

47、hen not in use, to minimize evaporation of the solvent.7.2.3 Internal standards working solution (10 mg/l of organotin cation)Use the pipette (5.6) to transfer 1,0 ml of the internal standard solution (7.2.2) into a 100 ml volumetric flask (5.8). Make the solution up to volume with methanol (4.13).T

48、his corresponds to a 10 mg/l working solution for the four internal standards.7.2.4 Target compounds stock solution (1 000 mg/l of organotin cation)Use the analytical balance (5.2) to weigh the appropriate amount of each target compound (see Table 1). Dissolve them together in methanol (4.13) in a s

49、ingle volumetric flask (5.8) of at least 100 ml to obtain the concentration of 1 000 mg/l for each substance. Store the standard solution for a maximum of one year in a fridge, when not in use, to minimize evaporation of the solvent.7.2.5 Target compounds working solution (10 mg/l of organotin cation)Use the calibrated pipette (5.6) to dispense 1,00 ml of the target compound stock solution (7.2.4) into a 100 ml volumetric flask (5.8). Make the solution up to volume with methanol (4.13).This corresponds to a 10 m