1、BRITISH STANDARD BS EN 13268:2001 Incorporating Corrigendum No. 1 Surface active agents Determination of ethylene oxide and propylene oxide groups in ethylene oxide and propylene oxide adducts The European Standard EN 13268:2001 has the status of a British Standard ICS 71.100.40 BS EN 13268:2001 Thi
2、s British Standard, having been prepared under the direction of the Sector Committee for Materials and Chemicals, was published under the authority of the Standards Committee and comes into effect on 15 June 2001 BSI 9 January 2004 ISBN 0 580 37403 3 National foreword This British Standard is the of
3、ficial English language version of EN 13268:2001, including Corrigendum July 2002. The UK participation in its preparation was entrusted to Technical Committee CII/34, Methods of test for surface active agents, which has the responsibility to: A list of organizations represented on this committee ca
4、n be obtained on request to its secretary. Additional information Some textual errors were discovered when the English language version of EN 13268:2001 was adopted as the national standard. Some of the chemical names are not consistently presented and do not conform to IUPAC recommendations.These t
5、extual errors have been reported to CEN in a proposal to amend the text of the European Standard. Cross-references The British Standards which implement international or European publications may be found in the BSI Standards Catalogue under the section entitled “International Standards Corresponden
6、ce Index”, or by using the “Find” facility of the BSI Standards Electronic Catalogue. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application. Compliance with a British Standard does not of it
7、self confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate th
8、em in the UK. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 15 and a back cover. The BSI copyright date displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. Date Comments 14
9、888 Corrigendum No. 1 9 January 2004 Correction to Clause 8 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13268 April 2001 ICS 71.100.40 Incorporating corrigendum July 2002 English version Surface active agents Determination of ethylene oxide and propylene oxide groups in ethylene oxide and p
10、ropylene oxide adducts Agents de surface Dtermination de la teneur en oxyde dthylne et en oxyde de propylne dans les condensats base doxyde dthylne et doxyde de propylne Grenzflchenaktive Stoffe Bestimmung von Ethylenoxid- und Propylenoxid-Gruppen in Ethylenoxid- und Propylenoxid-Addukten This Europ
11、ean Standard was approved by CEN on 19 January 2001. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references co
12、ncerning 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 responsibility of a CEN member into its own
13、 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, Malta, Luxembourg, Netherlands, Norway, Portugal, Slova
14、kia, 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 2001 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN
15、national Members. Ref. No. EN 13268:2001 EPage 2 EN 13268:2001 BSI 9 January 2004 Contents Page Foreword 3 Introduction 4 1 Scope. 5 2 Normative references. 5 3 Principle. 5 4 Reagents 5 5 Apparatus 6 6 Sampling and preparation of the test sample . 6 7 Procedure 7 8 Expression of results. 8 9 Precis
16、ion 9 10 Test report. 10 Annex A (informative) Ring test results (CESIO/AISE Ring test 408-1-92). 11 Bibliography. 15 Page 3 EN 13268:2001 BSI 9 January 2004 Foreword This European Standard has been prepared by Technical Committee CEN/TC 276, Surface active agents, the Secretariat of which is held b
17、y AFNOR. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by October 2001, and conflicting national standards shall be withdrawn at the latest by October 2001. Annex A is informative. According to the
18、 CEN/CENELEC 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, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sw
19、eden, Switzerland and the United Kingdom. Page 4 EN 13268:2001 BSI 9 January 2004 Introduction Under the specified reaction conditions, ethylene oxide groups convert stoichiometrically into ethyl iodide. However, the conversion of propylene oxide groups to isopropyl iodide is not stoichiometric. Pag
20、e 5 EN 13268:2001 BSI 9 January 2004 1 Scope This European Standard specifies a method for the qualitative and quantitative determination of ethylene oxide and propylene oxide groups in ethylene oxide (EO) and propylene oxide (PO) adducts, polyethers and polyglycol esters. NOTE If a suitable calibra
21、tion is performed, methoxy groups can also be determined. 2 Normative references This European Standard incorporates by dated or undated reference, provisions from other publications. These normative references are cited at the appropriate places in the text and the publications are listed hereafter
22、. 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 the latest edition of the publication referred to applies (including amendments). EN ISO 3696, Wate
23、r for analytical laboratory use Specification and test methods (ISO 3696:1987). ISO 607, Surface active agents and detergents Methods of sample division. ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and r
24、eproducibility of a standard measurement method. 3 Principle Hydroiodic acid and nonane are added to the sample to be analysed and the mixture is heated in a closed vessel for 1 h at 150 C. Upon conversion, ethylene oxide groups form stoichiometric amounts of ethyl iodide, and propylene oxide groups
25、 form 74 % to 77 % (m/m) of propyl iodide (mainly the iso-form, less frequently the n-form). These compounds are extracted by the nonane present and thus removed from the reaction medium. Under the specified digestion conditions, ethyl iodide is formed from all compounds containing ethoxy groups (et
26、hers and esters) and ethylene glycol derivatives; and isopropyl iodide is formed from all compounds containing isopropoxy groups, propylene glycol and glycerol derivatives. The alkyl iodides are determined directly from the nonane solution by means of gas chromatography using toluene as internal sta
27、ndard. Substances that contain isobutyl groups give isobutyl iodide when cleavage takes place. Isobutyl iodide cannot be exactly separated from the internal standard, toluene, in the chromatogram. 4 Reagents During the analysis, use only reagents of recognized analytical grade and water complying wi
28、th grade 3 as defined in EN ISO 3696. 4.1 Hydroiodic acid, HI, w(HI) 6,7 %. 4.2 Adipic acid, C 8 H 6 O 4 , w(C 8 H 6 O 4 ) 98 %. 4.3 Toluene, C 7 H 8 , w(C 7 H 8 ) 99 %. 4.4 Nonane, C 9 H 20 , wC 9 H 20 ) 99 %, GC quality. Page 6 EN 13268:2001 BSI 9 January 2004 4.5 Ethyl iodide, C 2 H 5 I, w(C 2 H
29、5 I) 99 %, GC quality. 4.6 Propyl iodide, C 3 H 7 I, w(C 3 H 7 I) 98 %. 4.7 Isopropyl iodide, C 3 H 7 I, w(C 3 H 7 I) 98 %. 4.8 Internal standard solution. Fill a 1 000 ml volumetric flask with about 200 ml nonane (4.4). Add approximately 2 g of toluene (4.3), weighed to nearest 0,01 g. Fill the fla
30、sk up to the mark with nonane. 4.9 2-phenoxyethanol, C 8 H 10 O 2 , w(C 8 H 10 O 2 ) 98 %. 4.10 1,2-propanediol, C 3 H 8 O 2 , w(C 3 H 8 O 2 ) 99 %. 5 Apparatus Ordinary laboratory apparatus and the following: 5.1 Metal heating block, thermostatically controlled, to fit the pressure resistant digest
31、ion vial (5.2), capable of maintaining a temperature of (150 5) C, or drying cupboard, capable of maintaining a temperature of (150 5) C. 5.2 Pressure resistant digestion vial for hydroiodic cleavage, for example as shown in Figure 1, with a screw top lined with a rubber septum onto which a protecti
32、ve polytetrafluorethylene foil is glued. 5.3 Syringes, with capacities of 1 l and 50 l. 5.4 Gas chromatograph, equipped with on-column injector and flame ionization detector (FID) or thermal conductivity detector (TCD). 5.5 Integrator, or computer-based chromatography data system. 5.6 Laboratory sha
33、ker, or magnetic stirrer suitable for the metal heating block (5.1). 6 Sampling and preparation of the test sample 6.1 General The sample shall be taken in accordance with ISO 607 and prepared as specified in 6.2. 6.2 Digestion Weigh approximately 50 mg of the test sample to the nearest 0,1 mg and t
34、ransfer it into the pressure resistant digestion vial (5.2). Add approximately 150 mg of adipic acid (4.2), 2 ml of hydroiodic acid (4.1) and 2 ml of internal standard solution (4.8). Add a stirring bar if the laboratory shaker or the magnetic stirrer (5.6) is used. Immediately seal the pressure res
35、istant digestion vial tightly and either place it into the metal heating block (5.1) set at (150 5) C (130 5) C if the laboratory shaker or the magnetic stirrer (5.6) is used or in the drying cupboard (5.1) set at (150 5) C. Maintain the corresponding temperature for 1,5 h 5 min 1 h 5 min in case of
36、 the metal heating block (5.1) without the laboratory shaker or the magnetic stirrer (5.6). Cool to room temperature. Page 7 EN 13268:2001 BSI 9 January 2004 Shake vigorously in order to obtain a phase separation. Inject with the 1 l syringe (5.3) 0,3 l of nonane phase into the gas chromatograph for
37、 the analysis. NOTE 1 Strict adherence to the specified conditions is important because the digestion is relatively sensitive to temperature variations. NOTE 2 The fully digested samples can be kept sealed up to 38 h at 4 C. Older or tapped test samples give misleading results. 7 Procedure 7.1 Chrom
38、atography conditions Detector: FID or TCD; Injector: on-column; Carrier gas: helium; Column: fused silica capillary column, coated with a stationary phase of 3 % volume units of cyanopropylpolysiloxane/3 % volume units of phenylpolysiloxane/94 % volume unit of methyl polysiloxane; length: 30 m; inte
39、rnal diameter: 0,25 mm; film thickness: 1 m; Temperature programme: 60 C, 3 min isothermal; 60 C to 130 C, 6 C/min; 130 C to 280 C, 15 C/min; 280 C, 20 min isothermal. Injector temperature: 130 C; Detector temperature: 200 C. NOTE If the separation is comparable to that demonstrated by the chromatog
40、ram as shown in Figure 2, different instruments, columns and conditions can also be used for the GC analysis. 7.2 Calibration Add the following substances in sequence to the pressure resistant digestion vial (5.2): about 50 mg of adipic acid (4.2); 2,00 ml of internal standard solution (4.8); 2 ml o
41、f hydroiodic acid (4.1). Page 8 EN 13268:2001 BSI 9 January 2004 Use the 50 l syringe (5.3) to introduce 50 l of isopropyl iodide (4.7) or 45 l of ethyl iodide (4.5) (about 100 mg) through the septum. Weigh the vial, then shake vigorously. NOTE Phase separation is allowed to occur. 7.3 Determination
42、 Chromatograph the test samples and calculate the response factors as specified in 7.4. NOTE Daily recalibration is unnecessary. The accuracy of the response factors can be monitored with the help of test samples prepared from defined amounts of 2-phenoxyethanol and 1,2-propanediol. For the determin
43、ation of methoxy groups, methyl iodide should be used for calibration and test samples prepared from defined amounts of vanillin minimum purity of 99 % (m/m) for monitoring the accuracy of the response factors. 7.4 Calculation The results are calculated using the internal standard method to derive t
44、he relative response factors. Calculate the relative response factors (f i ) from the equation (1): o o i i i /F m /F m f = (1) where: m iis the mass of alkyl iodide in the calibrating solution, in grams; m ois the mass of the internal standard in the calibrating solution, in grams; F iis the peak a
45、rea of the alkyl iodide in the calibrating solution, in peak area units; F ois the peak area of the internal standard, in peak area units. The factors shall be determined with pure alkyl iodides. 8 Expression of results Calculate the content of ethylene oxide w(EO) and propylene oxide w(PO), express
46、ed as percent by mass, using the equations (2) to (4) as follows: o o i i i m F F f m = (2) 100 EO I 5 H 2 C EO i = M M m m ) ( w (3) 33 1 100 PO I 7 H 3 C PO i , ) ( = M M m m w (4) Page 9 EN 13268:2001 BSI 9 January 2004 where: m iis the mass of alkyl iodide in the calibrating solution, in grams;
47、m ois the mass of the internal standard in the calibrating solution, in grams; m is the initial mass of the test sample, in grams; M EOis the molar mass of EO, in grams per mol (M EO= 44,05 g/mol); M C 2 H 5 Iis the molar mass of C 2 H 5 I, in grams per mol (M C 2 H 5 I= 155,97 g/mol); M POis the mo
48、lar mass of PO, in grams per mol (M PO= 58,08 g/mol); M C 3 H 7 Iis the molar mass of C 3 H 7 I, in grams per mol (M C 3 H 7 I= 169,99 g/mol); 1,33 is a correction factor. Calculate the sum of n- and isopropyl iodide. Express the results to one decimal place. NOTE 1 The correction factor accounts fo
49、r the incomplete transformation of the propylene oxide groups. It is a constant and does not depend on the particular reaction conditions used. NOTE 2 Under the given conditions, a baseline separation of the alkyl iodides is observed so that there is no need for involving correction calculations. 9 Precision 9.1 Repeatability limit The absolute difference between two independent single
