1、| | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | | BRITISH STANDARD BS EN 12582:1999 The Euro
2、pean Standard EN 12582:1999 has the status of a British Standard ICS 71.100.40 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW Surface active agents Determination of the polyethylene glycol content according to molar mass in non-ionic surface active agents (ethoxylated) by HPL
3、C/ELSDThis 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 September 1999 BSI 09-1999 ISBN 0 580 32286 6 BS EN 12582:1999 Amendments issued since p
4、ublication Amd. No. Date Comments National foreword This British Standard is the English language version of EN 12582:1999. 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: aid enquirers t
5、o 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 them in the UK. A list of organizations represented on this co
6、mmittee can be obtained on request to its secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence Index”, or by
7、 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 itself confer immu
8、nity from legal obligations. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 7 and a back cover The BSI copyright notice displayed in this document indicates when the document was last issued.CEN European Committee for Standardization Comi
9、te Europe en de Normalisation Europa isches Komitee fu r Normung Central Secretariat: rue de Stassart 36, B-1050 Brussels 1999 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 12582:1999 E EUROPEAN STANDARD EN 12582 NORME EUROPE ENN
10、E EUROPA ISCHE NORM March 1999 ICS Descriptors: surfactants, non-ionic surfactants, chemical analysis, determination of content, polyethylene, glycol, condensates, ethylene oxide, chromatography, high performance liquid chromatography English version Surface active agents Determination of the polyet
11、hylene glycol content according to molar mass in non-ionic surface active agents (ethoxylated) by HPLC/ELSD Agents de surface De termination de la teneur en polye thyle ne glycol en relation avec leur masse molaire dans les agents de surface non ioniques (condensats doxyde de thyle ne) par CLHP/DEDL
12、 Grenzfla chenaktive Stoffe Bestimmung des Gesamtgehaltes an Polyethylenglycol in nichtionischen grenzfla chenaktiven Stoffen (Ethoxylaten) nach molarer Masse mittels HPLC/ELSD This European Standard was approved by CEN on 13 February 1999. CEN members are bound to comply with the CEN/CENELEC Intern
13、al 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 concerning such national standards may be obtained on application to the Central Secretariat or to any CEN member.
14、 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 language and notified to the Central Secretariat has the same status as the official versions. CEN members ar
15、e the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom.Page 2 EN 12582:1999 BSI 09-1999 Foreword This European Standard has been
16、prepared by Technical Committee CEN/TC 276, Surface active agents, 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 identical text or by endorsement, at the latest by September 1999, and conflicting nation
17、al standards shall be withdrawn at the latest by September 1999. Annex A is informative. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finlan
18、d, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom.Page 3 EN 12582:1999 BSI 09-1999 1 Scope This European Standard specifies a method for the determination of the polyethylene glycol (PEG) content in aroma
19、tic and aliphatic non-ionic surface active agents of the type R-(O-C 2 H 4 ) p OH; where p is the mean ethylene oxide (EO) value. It is applicable to all ethoxylated products soluble in methanol or methanol/water mixture. This method applies to PEG concentrations as mass fraction greater than or equ
20、al to 0,1 %. The method is not applicable to PEG whose molar mass is lower than 400 g/mol. Monomeric ethylene glycol, diethylene glycol, triethylene glycol and glycerol are not detected. NOTE Evaporative light scattering detector (ELSD) is convenient for routine methods. 2 Normative references This
21、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. For dated references, subsequent amendments to or revisions of any of these publicat
22、ions 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. EN ISO 3696, Water for analytical laboratory use Specification and test methods. (ISO 3696:1987) ISO 607:1980, Surface active
23、agents and detergents Methods of sample division. ISO 5725-2:1994, 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. ISO 6353-2:1983, Reagents for chemical analysis Pa
24、rt 2: Specifications First series. 3 Principle Polyethylene glycol is separated from the polyethoxylated surface active agents by means of reversed phase liquid chromatography. In this process PEG is eluted in the first minutes while the non-ionic surface active agents are retarded. Evaporative ligh
25、t scattering detector (ELSD) does not detect volatile materials such as the sample solvent; interferences with the PEG peak are limited. The sample is dissolved in an 80/20 (V/V) mixture of methanol/water or in another methanol/water mixture to obtain a clear solution. A portion of the sample soluti
26、on is then analysed by high performance liquid chromatography (HPLC). Quantification of PEG content is achieved by external calibration with PEG molar mass equal to 1 000 g/mol. 4 Reagents All reagents shall be of a recognized analytical grade if not listed in ISO 6353-2 and the water used shall con
27、form to grade 3 in accordance with EN ISO 3696. 4.1 Polyethylene glycol, with molar mass of 1 000 g/mol, gel permeation chromatography (GPC) grade. 4.2 Methanol, HPLC grade, filtered before use with filter unit (5.5). 4.3 Water, HPLC grade, filtered before use with filter unit (5.5). 4.4 Helium gas,
28、 chromatography grade, for degassing eluent. 4.5 Nitrogen or air, dry and without dust. 4.6 Mobile phase, either: a) 80/20 (V/V) mixture of methanol and water; or b) methanol. 5 Apparatus Ordinary laboratory apparatus and glassware with the following. 5.1 HPLC unit, equipped with gradient pump. 5.2
29、Evaporative light scattering detector (ELSD). 5.3 Chromatography column, octadecyl C18 bonded phase silica gel; 5mm; 250 mm length and 4,6 mm internal diameter. 5.4 Data logger/plotter, capable of recording and displaying the chromatographic peak area. 5.5 Filter unit, for solvent (0,45mm). 5.6 Syri
30、nges, 10 ml. 6 Sampling 6.1 Preparation of the test sample Prepare and store the test sample in accordance with ISO 607. 6.2 Preparation of test solutions Weigh, to the nearest 0,1 mg, the test sample mass given in Table 1 for the expected PEG content into a 25 ml volumetric flask. Fill to the mark
31、with the mobile phase 4.6.a) or other suitable mixture of methanol/water and dissolve to obtain a clear solution. If necessary, filter through 0,45mm filter unit. Table 1 Expected PEG Sample mass for 25 ml solution % 2,5 a) 0,1 to 2 2,5 2t o5 1 5 to 10 0,5 10 to 25 0,2 a) But not exceeding the sampl
32、e solubility limits.Page 4 EN 12582:1999 BSI 09-1999 7 Procedure 7.1 Apparatus settings Set the HPLC unit according to the following conditions. 7.1.1 Gradient a) t = 0 min 0 % methanol 4.6b); b) t = 6 min 0 % methanol 4.6b); c) t = 7 min 100 % methanol 4.6b); d) t = 30 min 100 % methanol 4.6b); e)
33、t = 35 min 0 % methanol 4.6b). NOTE Going from mobile phase 4.6a) to mobile phase 4.6b) is done in order to elute the ethoxylated products more rapidly. 7.1.2 Flow rate: 1,0 ml/min. 7.1.3 Temperature: room temperature. 7.1.4 Injection volume: 20ml. 7.1.5 Detector: evaporative light scattering detect
34、or (ELSD). Optimize the working conditions, depending on the apparatus in use and the physical parameters (nebulization temperature and working pressure). 7.2 Calibration 7.2.1 Preparation of calibration solutions Weigh, to the nearest 0,1 mg, 0,025 g, 0,05 g, 0,1 g and 0,2 g of polyethylene glycol
35、(PEG 1000) (4.1) each into 100 ml volumetric flasks, dissolve in the mobile phase 4.6.a) and make up to the mark. These solutions respectively correspond to 0,25 %, 0,5 %, 1 % and 2 % of PEG in a test sample of 2,5 g in 25 ml of mobile phase. NOTE Calibration curves with PEG 400, 1 500 and 2 000 giv
36、e similar results to PEG 1 000. Curve shifts are observed from PEG 4 000, 6 000 and 8 000. For PEG 10 000, the calibration curve is not linear. Mix the solution thoroughly. If necessary, filter through a 0,45mm filter unit. 7.2.2 Calibration curve Analyse, at least twice, calibration solutions prepa
37、red in 7.2.1, in accordance with the chromatographic conditions given in 7.1. Construct a graph: log of peak area (y-axis) versus log PEG weight in 25 ml (x-axis) and draw a calibration curve. 7.3 Determination Take the test solution as prepared in 6.2 and carry out the analysis in accordance with t
38、he chromatographic conditions given in 7.1. Typical chromatograms are shown in Figures A.1 and A.2. NOTE In this “reversed phase HPLC” method, polyethylene glycol elutes quickly in the first minutes, in only one peak. When the molar mass distribution of PEG is large, it is possible to observe severa
39、l peaks or shoulders corresponding to different molar masses of PEG. Sum the peak areas of the chromatogram corresponding to PEG. 8 Expression of results Use the calibration curve 7.2.2 to obtain the PEG mass corresponding to the area given by the integrator. Express the PEG content as mass fraction
40、 in percent as follows: % PEG = m3 100 m 0 where m 0 is the mass of sample to be analysed (6.2), in grams; m is the mass of PEG determined by means of the calibration curve, in grams. 9 Precision 9.1 Repeatability The absolute difference between two single test results obtained under repeatability c
41、onditions according to ISO 5725-2 shall not be greater than 0,3 % (mass fraction), with a probability of 95 %. The repeatibility conditions are conditions where mutually independent test results are obtained with the same method on identical test material in the same laboratory by the same operator
42、using the same equipment within short intervals of time. Results of an interlaboratory test carried out in accordance with ISO 5725-2 are given in annex A. 9.2 Reproducibility The absolute difference between two single test results obtained under reproducibility conditions according to ISO 5725-2 sh
43、all not be greater than 1,7 % (mass fraction) with a probability of 95 %. The reproducibility conditions are conditions where test results are obtained with the same method on identical test material in different laboratories with different operators using different equipment. Results of an interlab
44、oratory test carried out in accordance with ISO 5725-2 are given in annex A. 10 Test report The test report shall include the following information: a) all information necessary for the complete identification of the sample; b) a reference to this European Standard; c) the results with their units (
45、see clause 8); d) room temperature for each liquid chromatographic determination and all information about ELSD detector; e) details of any operations not specified in this European Standard or in the International Standards to which reference is made, and any operations regarded as optional, as wel
46、l as any incidents likely to have affected the results.Page 5 EN 12582:1999 BSI 09-1999 Annex A (informative) Interlaboratory test results The interlaboratory test results were obtained in the framework of CESIO activity in 1993. Sample 1 Branched chain alcohol ethoxylate (near 5 EO) Laboratory Numb
47、er of single values Mean value Standard deviation 1 2 1,0 0 2 3 1,06 0,038 3 2 0,84 0,014 4 2 0,95 0,071 5 2 1,10 0,035 6 2 0,75 0,028 7 5 0,92 0,019 8 2 0,92 0,014 9 10 2 0,92 0 11 3 1,04 0,022 12 3 0,95 0,026 13 6 1,08 0,072 14 4 0,64 0,021 15 6 0,80 0,023 Number of laboratories retained after eli
48、minating outliers 14 Number of outliers (laboratories) 1 Number of accepted results 41 Mean value (g/100 g sample) 0,95 Repeatability standard deviation s r (g/100 g sample) 0,039 3 Repeatability limit: r = 2,8 s r (g/100 g sample) 0,110 Repeatability relative standard deviation (%) 4,14 % Reproduci
49、bility standard deviation s R (g/100 g sample) 0,144 4 Reproducibility limit: R = 2,8 s R (g/100 g sample) 0,404 Reproducibility relative standard deviation (%) 15,2 % Sample 2 Long chain alcohol ethoxylate (near 50 EO) Laboratory Number of single values Mean value Standard deviation 1 2 3,3 0 2 3 3,06 0,081 3 2 2,43 0,021 4 2 3,55 0,071 5 2 3,91 0,099 6 2 2,69 0,156 7 5 3,30 0,079 8 2 1,99 0,085 9 1 0 11 3 3,78 0,061 12 3 2,85 0,116 13 9 3,86 0,066 14 4 2,57 0,224 15 6 3,20 0,026 Number of laboratorie
