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 16179:2012Copyright E
2、uropean Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-National forewordThis Published Document is the UK implementation of CEN/ISO TS 16179:2012.The UK participation in its preparation was entrus
3、ted 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.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct app
4、lication. 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 immunity from legal obligations.This Published Document was published under the authority of the Standards Policy and Strategy Com
5、mittee on 31 August 2012.Amendments issued since publicationDate Text affectedPUBLISHED DOCUMENTPD CEN/ISO TS 16179:2012Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-TECHNICAL
6、SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE 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 - S
7、ubstances critiques potentiellement prsentes 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 zinno
8、rganischer Verbindungen in Schuhwerkstoffen (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 s
9、ubmit their comments, particularly on the 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 pe
10、rmissible to keep conflicting national standards 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, Est
11、onia, Finland, Former Yugoslav Republic 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 STA
12、NDARDIZATION COMIT EUROPEN DE NORMALISATION 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 16179:2012Copyr
13、ight European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-CEN ISO/TS 16179:2012 (E) 2 Contents Page Foreword 3PD CEN/ISO TS 16179:2012Copyright European Committee for Standardization Provided b
14、y IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-CEN 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 coll
15、aboration with Technical Committee ISO/TC 216 “Footwear“. Attention is drawn to 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
16、 Internal Regulations, the national standards organisations of the following countries 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,
17、Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. PD CEN/ISO TS 16179:2012Copyright European Committee for Standardization Provided by IHS under license with CE
18、NNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO/TS 16179:2012(E) ISO 2012 All rights reserved iiiContents Page1 Scope 12 Normative references . 13 Principle . 14 Reagents 15 Apparatus and materials . 26 Preparation of the test piece 37 Procedure 37.1 Preparati
19、on 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 . 67.8 Gas chromatography 67.9 Quantification . 7
20、7.10 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/ISO TS 16179:2012Copyright European Committee for
21、 Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-TECHNICAL SPECIFICATION ISO/TS 16179:2012(E)Footwear Critical substances potentially present in footwear and footwear components Determination of organotin compou
22、nds in footwear materials1 ScopeThis Technical Specification specifies a test method for determining the presence of organotin 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 refere
23、ncesISO 3696, Water for analytical laboratory use Specification and test methods3 PrincipleThe organotin substances are 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 organo
24、tin is then converted to the corresponding volatile tetra-alkyl derivative, by reaction with sodium tetraethylborate, NaB(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
25、Technical Specification.Table 1 List of target compounds which can be analysed with this Technical SpecificationType of compound Compound CASaMonosubstitutedn-butyltin trichloride 1118- 46-3n-octyltin trichloride 3091-25-6DisubstitutedDi-n-butyltin dichloride 683-18-1Di-n-octyltin dichloride 3542-36
26、-7TrisubstitutedTri-n-butyltin chloride 1461-22-9Triphenyltin chloride (or fentin chloride) 639-58-7Tricyclohexyltin chloride 3091-32-5Tetrasubstituted Tetra-n-butyltin 1461-25-2aChemical Abstract Service.4 ReagentsUnless otherwise specified, use only reagents of recognized analytical grade.4.1 Wate
27、r, grade 3 according to ISO 3696.4.2 Ethanol, GPR grade or industrial methylated spirit (IMS), CAS number: 64-17-5.4.3 Glacial acetic acid, CAS number: 64-19-7. ISO 2012 All rights reserved 1PD CEN/ISO TS 16179:2012Copyright European Committee for Standardization Provided by IHS under license with C
28、ENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO/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).4.7 Di-n-he
29、ptyltin 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.4.12 Tropolo
30、ne (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 with a mass s
31、elective 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 sealing the
32、 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 flasks of 1
33、0 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 16179:2012Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleN
34、o reproduction or networking permitted without license from IHS-,-,-ISO/TS 16179:2012(E)5.13 Mechanical shaker, adjusted to a minimum frequency of 50 min1.6 Preparation of the test pieceThe test piece consists of a single material taken from the footwear, such as leather, textile, polymer, coated ma
35、terial 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, which results in particles with a maximum diameter of 4 mm or less.7 ProcedureSAFETY PRECAUTIONS Sodium tetraethylborate solution shall be prep
36、ared 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 fume cupboard, using the method provided, in order to minimize fire risks. Organotins are both toxic and known endocrine system disrupters;
37、 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 before an aliquot is taken.7.1 Preparation of the sodium tetraethylborate solution7.1.1 Preparation shall be carried out in an inert environme
38、nt.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 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
39、 (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 through the side of the inert environment, fill the bag with gas, allowing mixed air and inert gases to be expelled through the front opening
40、 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 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 tetraethylbora
41、te (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 bottle.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
42、 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 maximum of three months in a fridge, when not in use, to minimize evaporation of the solvent.NOTE Pre-weighed tetraethylborate or commercial so
43、lutions are available on the market. ISO 2012 All rights reserved 3PD CEN/ISO TS 16179:2012Copyright European Committee for Standardization Provided by IHS under license with CENNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO/TS 16179:2012(E)7.2 Preparation of
44、standard solutions7.2.1 GeneralThe 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 c
45、hloride form and Bu2Sn2+is the 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 W
46、eighting factorAmount of organotin 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 c
47、hloride 0,891 112,2Triphenyltin 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 1
48、60,5 mg of monobutyltin trichloride (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 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 org
