1、Packaging - Flexible packaging material - Determination of residual solvents by static headspace gas chromatography - Part 1: Absolute methods The European Standard EN 13628-12002 has the status of a British Standard ICs 55.040 BS EN 1362 8-1 :20 02 NO COPYING WITHOUT BCI PERMISSION EXCEPT AS PERMIT
2、TED BY COPYRIGHT LAW British Standards BS EN 13628-k2002 Amd. No. National foreword Date Comments This British Standard is the official English language version of The UK participation in its preparation was entrusted by Technical Committee PKWl5, Primary and transport packaging, to Subcommittee PKw
3、15126, Packaging made from flexible materials, which has the responsibility to: EN 13628-1:2002. - - aid enquirers to understand the text; present to the responsible internationaUEuropean committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; moni
4、tor related international and European developments and promulgate them in the UK. - A list of organizations represented on this subcommittee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this
5、 document may be found ir, the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online. This publication does not purport to include all the necessary provisions of a con
6、tract. Users are responsible for its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. This British Standard, having been prepared under the direction of the Consumer products and services sector was published under the authority of th
7、e Standards Policy and Strategy Committee on 21 October 2002 Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 16, an inside back cover and a back cover. The BSI copyright date displayed in this document indicates when the Committee2 documen
8、t was last issued. O BSI 21 October 2002 ISBN O 580 40627 X EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 1362%-a October 2002 ICs 55.040 English version Packaging - Flexible packaging material - Determination of residual solvents by static headspace gas chromatography - Part I : Absolute met
9、hods Emballage - Matriaux demballages souples - Dtermination des solvants rsiduels par chromatographie en phase gazeuse et espace de tte statique - Partie 1: Mthodes absolues Verpackung - Flexible Packstoffe - Bestimmung der Restlsemittel durch statische Dampfraumanalyse mittels Gaschromatographie -
10、 Teil 1: Absolute Verfahren This European Standard was approved by CEN on 26 August 2002. CEN members are bound to comply with the CENICENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date li
11、sts and bibliographical references concerning such national standards may be obtained on application to the Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the respon
12、sibility of a CEN member into its own language and notified to the Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland. Ireland, Italy, Luxembourg, Malta,
13、 Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels O 2002 CEN All rights of exploitation in any form and by any mean
14、s reserved worldwide for CEN national Members. Ref. No. EN 13628-1:2002 E EN 13628-1 2002 (E) Contents Page Foreword 3 1 Scope 4 2 Normative references 4 3 Principle 4 4 Reagents . 4 5 Apparatus . 5 6 Sampling . 8 7 Test specimens 8 8 Incubation of the test specimens . 8 9 Procedure . 9 10 Precision
15、 data . 16 11 Test report 16 2 EN 13628-1 2002 (E) Foreword This document EN 13628-1 :2002 has been prepared by Technical Committee CENTTC 261 “Packaging“, the secretariat of which is held by AFNOR. This European Standard shall be given the status of a national standard, either by publication of an
16、identical text or by endorsement, at the latest by April 2003, and conflicting national standards shall be withdrawn at the latest by April 2003. This standard is part of a standard for determination of residual solvents by static headspace gas chromatography, which is published in two parts: - Part
17、 I: Absolute methods - Part 2: Industrial methods According to the CENKENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ire
18、land, Italy, Luxembourg, Malta, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom. 3 EN 13628-1:2002 (E) 1 Scope This part of this European Standard specifies methods for the quantitative determination of residual solvents in flexible packaging by static headspace chro
19、matography where the chemical identities of the residual solvents to be determined are known before commencing the analysis. Residues from thermal decomposition products are not within the scope of this standard. The method is applicable to flexible packaging materials that may consist of mono- or m
20、ultilayer plastic films, paper or board, foil or combinations thereof. This method does not apply to residual solvents with amounts lower than 0,5 mg/m2. 2 Normative references This European Standard incorporates by dated or undated reference, provisions from other publications. These normative refe
21、rences are cited at the appropriate places in the text, and the publications are listed hereafter. For dated references, subsequent amendments to or revisions of any of these publications apply to this European Standard only when incorporated in it by amendment or revision. For undated references th
22、e latest edition of the publication referred to applies (including amendments). IS0 5725-2, Accuracy (trueness and precision) of measurement methods and results - Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method. 3 Principle Specimens o
23、f the flexible packaging material are placed in a hermetically closed vial and heated under closely controlled conditions of time and temperature to vaporize solvents into the headspace. The amount of solvent released into the headspace is determined by transferring an aliquot of the headspace into
24、a gas chromatograph for analysis. The transfer may be performed: a) by specific semi-automatic or automatic systems which allow pressurization of the heated vials. Quantification is achieved by the multiple headspace extraction (MHE) procedure using external or internal standards; b) manually or aut
25、omatically by using a heated gastight syringe or a loop without pressurization of the heated vials. Quantification is achieved by the standard addition method. NOTE A prerequisite for a quantitative determination of residual solvents by headspace gas chromatography is that a partition equilibrium fo
26、r the solvent between the gas phase and the solid phase has been reached before an aliquot of the headspace is withdrawn and transferred into the gas chromatograph. During the analysis, there may be interferences from possible products of thermal decomposition. Additional peaks due to these products
27、 shall not be considered for evaluation of residual solvents. 4 Reagents 4.1 General All reagents shall be of a recognized analytical reagent grade. NOTE Grades stated as being suitable for chromatography are commercially available and are recommended for use as reference for standard calibration so
28、lutions. Appropriate safety precautions should be used when handling toxic and/or flammable solvents. 4 EN 13628-1 2002 (E) 4.2 Reference solvents, for the preparation of standard calibration solutions. 4.3 Dilution solvent, with a retention time different from those of residual solvents in the samp
29、le. NOTE Solvents such as hexane, cyclohexanone, acid amides and glycerol triacetate (triacetin) are appropriate. 5 Apparatus 5.1 Glass vials, of capacity 6 ml, 8 ml, 20 ml, 50 ml or 100 ml depending upon the specific requirements of accessory equipment, for example, the headspace sampler, fitted wi
30、th an inert septum seal and aluminium crimp tops. The septum seal shall neither absorb nor release volatile components, shall be gas tight during incubation and shall permit samples of the headspace gas to be withdrawn by syringe for subsequent analysis. NOTE Elastomers lined with polytetrafluoroeth
31、ylene (PTFE) are suitable materials for septum seals. 5.2 Crimping tool, for sealing the vials with the aluminium crimp tops. 5.3 Seal removing tool. 5.4 Analytical balance, capable of weighing to the nearest 0,l mg. 5.5 Template, for cutting samples. The dimensions of this template shall be matched
32、 to the vial volume used. 5.6 Scalpel or sharp knife. 5.7 Syringes (e.g. 1 pi, 10 pi). 5.8 Gas chromatograph, having a flame ionization detector or equivalent for the solvents to be determined. 5.9 Gas chromatographic column, either packed or capillary, that will give good resolution of the solvents
33、 to be determined from any other components that might be injected with the specimen of the headspace. Examples for suitable columns and operation conditions are: a) Packed column: length: 3 m; internal diameter: 3,2 mm; column filling: 80/120 mesh graphitised carbon, deactivated with polyethylenegl
34、ycol; carrier gas: N2, 20 ml/min; injector temperature: 220 OC; temperature programme: 80 OC; raised to 160 “C at 6 Wmin; raised to 225 “C at 13 “Clmin; held for 16 min; NOTE 1 A corresponding chromatogram obtained for a mixture of solvents is shown in Figure 1. 5 EN 13628-1 2002 (E) B 23 4 7 9 A Ke
35、y 1 4,23 methanol 2 6,67 ethanol 3 9,25 acetone 4 17, 06 ethyl acetate 5 19,l butanol 6 23,34 trichloroethylene 7 28,4 isobutyl acetate 8 33,87 methyl isobutylketone 9 41,86 toluene 1 O 64.06 xylene A Retention time (min) B Peak height Figure 1 - Example of chromatogram obtained with a packed column
36、 or b) Capillary column (fused silica): length: 30 m; internal diameter: 0,32 mm; stationary phase: Poly(dimethylsiloxane), film thickness 3 pm; carrier gas: He, 1,7 ml/min; 6 EN 13628-1 2002 (E) carrier gas split ratio: 1 :20; injector temperature: 230 “C; detector (flame ionization) temperature: 2
37、80 OC; temperature programme: 50 “C held for 5 min; raised to 100 “C at 5 “C/min raised to 250 “C at 10 “Clmin. NOTE 2 A corresponding chromatogram for a mixture of solvents is shown in Figure 2. B 1 1 3 4 5 2.5 05 7,5 Key 1 Methanol 2 Ethanol 3 Isopropanol 4 Methylethyl ketone 5 Ethyl acetate 6 Iso
38、butanol 7 Isopropyl acetate 8 n-propyl acetate 9 Methylisobutyl ketone 10 Ethoxypropanol 11 Toluene 12 n-butyl acetate 13 Xylene 14 Butyl cellosolve A Retention time (min) 8 Peak height 6 7 10 12,5 A g 11 12 13 14 4 15 17,5 20 L 22,5 Figure 2 - Example of chromatogram obtained with a capillary colum
39、n EN 13628-1 :2002 (E) NOTE 3 Other apparatus which is more specific to the alternative methods is identified under the relevant clauses. 6 Sampling Samples of packaging materials that are to be analysed shall be handled and stored so as to prevent either loss of volatile solvents or contamination b
40、y absorption of volatile solvents that may be present in the surrounding atmosphere. Sampling and analysis shall be done in a place where the air is solvent-free in order to reduce the problem of contamination of the samples from their surroundings due to the low concentrations of residual solvents
41、in the samples. NOTE Samples should be in tightly packed roll form if possible. Sheet samples can be prepared from the roll by cutting out a square window (several layers of sheets) with a knife. At least the first five layers should be discarded. When in the form of sheets they should be stacked ti
42、ghtly together to form a compact “block“ and wrapped tightly in a barrier material, preferably aluminium foil with a thickness of 30 pm to 40 pm. For storage periods of more than one hour the wrapped samples should be stored at temperatures below 5 “C and in an atmosphere free of volatile contaminan
43、ts. 7 Test specimens 7.1 Specimen area in relation to vial volume The specimen area to be cut out shall depend on the vial volume and the level of residual solvents to be determined in the material. The ratio between the specimen area (in cm2) and the vial volume (in mi) shall be between three and f
44、ive. The specimens shall be cut out using an appropriate template (5.5). NOTE proportional dimensions for other volumes. As an example for a vial with a volume of 6 rnl to 9 rnl a specimen of 30 cm2 (2 cm x 15 cm) can be used or 7.2 Test specimens from sheets From the top of the sample take a block
45、of about 15 to 20 sheets out without separating them. Immediately put back the remaining part of the sample in its packaging under the conditions specified in clause 6. Prepare a first vial; after withdrawal of at least one layer (or more depending on the number of specimens to be prepared from the
46、block) from the top of the block take the following sheet and rapidly cut the first specimen using a template (5.5). Coil the specimen rapidly and immediately put it into the vial. Crimp the vial immediately to seal it. Prepare further Specimens in the same way. The following precautions shall be ta
47、ken. The different steps of the preparation shall be done very rapidly to avoid evaporation of the solvents. The sample sheet from which the specimen is cut shall be taken out of the block immediately before preparation. The specimens shall always be cut at a defined place e.g. on the same drawing p
48、rinted on the same place in the width and the template for cutting shall always be placed in the same manner. 8 Incubation of the test specimens 8.1 General Incubation time and temperature shall be optimized for each individual system in order to achieve a partition equilibrium of the residual solve
49、nts between the solid phase and the gas phase. With a certain temperature selected an optimum heating time shall be determined. 8 EN 13628-1 2002 (E) NOTE 1 absorptive properties of the materials to be analysed. The time taken to reach partition equilibrium will vary for different solvents depending on the boiling point and the NOTE 2 As ar! initial guidance incubation, a temperature uf 100 “C for 60 min can be appropriate. However other incubation conditions depending on the materials and solvents to be analysed are also commonly used, e.g. temperature between 80 “C and
