1、BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06Plastics Aromatic isocyanates for use in the production of polyurethanes Determination of the isomer ratio in toluenediisocyanate (TDI)BS ISO 15064:2017 ISO 2017Plastics Aromatic isocyanates for use in the production of
2、 polyurethanes Determination of the isomer ratio in toluenediisocyanate (TDI)Plastiques Isocyanates aromatiques pour utilisation dans la production de polyurthannes Dtermination du rapport des isomres dans le diisocyanate de tolune (TDI)INTERNATIONAL STANDARDISO15064Third edition2017-06Reference num
3、berISO 15064:2017(E)National forewordThis British Standard is the UK implementation of ISO 15064:2017. It supersedes BS ISO 15064:2010, which is withdrawn.The UK participation in its preparation was entrusted to Technical Committee PRI/42, Fibre reinforced thermosetting plastics and prepregs.A list
4、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 application. The British Standards Institution 2017 Published by BSI Standards Lim
5、ited 2017ISBN 978 0 580 93948 8ICS 83.080.10Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 July 2017.Amendments/corrigenda issued since publicationDate Text
6、affectedBRITISH STANDARDBS ISO 15064:2017 ISO 2017Plastics Aromatic isocyanates for use in the production of polyurethanes Determination of the isomer ratio in toluenediisocyanate (TDI)Plastiques Isocyanates aromatiques pour utilisation dans la production de polyurthannes Dtermination du rapport des
7、 isomres dans le diisocyanate de tolune (TDI)INTERNATIONAL STANDARDISO15064Third edition2017-06Reference numberISO 15064:2017(E)BS ISO 15064:2017ISO 15064:2017(E)ii ISO 2017 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2017, Published in SwitzerlandAll rights reserved. Unless otherwise specif
8、ied, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address below or ISO
9、s member body in the country of the requester.ISO copyright officeCh. de Blandonnet 8 CP 401CH-1214 Vernier, Geneva, SwitzerlandTel. +41 22 749 01 11Fax +41 22 749 09 47copyrightiso.orgwww.iso.orgBS ISO 15064:2017ISO 15064:2017(E)Foreword iv1 Scope . 12 Normative references 13 Terms and definitions
10、. 14 Sampling 25 Principle 25.1 Method A 25.2 Method B 26 Reagents 27 Apparatus . 38 Test conditions . 39 Method A Samples containing between 5 % and 95 % of 2,6-TDI . 39.1 Calibration 39.2 Procedure 59.3 Expression of results 59.4 Precision and bias 59.4.1 Precision 59.4.2 Bias 59.5 Test report . 6
11、10 Method B Samples containing 0 % to 5 % of 2,6-TDI 610.1 Calibration 610.2 Procedure 610.3 Expression of results 610.4 Precision and bias 710.4.1 Precision 710.4.2 Bias 710.5 Test report . 7Annex A (normative) Calibration curves 8 ISO 2017 All rights reserved iiiContents PageBS ISO 15064:2017ISO 1
12、5064:2017(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject fo
13、r which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on
14、all matters of electrotechnical standardization.The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted.
15、This document was drafted in accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www .iso .org/ directives).Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying a
16、ny or all such patent rights. Details of any patent rights identified during the development of the document will be in the Introduction and/or on the ISO list of patent declarations received (see www .iso .org/ patents).Any trade name used in this document is information given for the convenience o
17、f users and does not constitute an endorsement.For an explanation on the voluntary nature of standards, the meaning of ISO specific terms and expressions related to conformity assessment, as well as information about ISOs adherence to the World Trade Organization (WTO) principles in the Technical Ba
18、rriers to Trade (TBT) see the following URL: www .iso .org/ iso/ foreword .html.This document was prepared by Technical Committee ISO/TC 61, Plastics, Subcommittee SC 12, Thermosetting materials.This third edition cancels and replaces the second edition (ISO 15064:2010), which has been technically r
19、evised.The main changes compared to the previous edition are as follows: a NOTE has been added to 6.2; the testing temperature has been added in Clause 8.iv ISO 2017 All rights reservedBS ISO 15064:2017INTERNATIONAL STANDARD ISO 15064:2017(E)Plastics Aromatic isocyanates for use in the production of
20、 polyurethanes Determination of the isomer ratio in toluenediisocyanate (TDI)WARNING Persons using this document should be familiar with normal laboratory practice. This document does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the
21、user of this document to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions prior to use.1 ScopeThis document specifies methods for the measurement of toluene-2,6-diisocyanate in mixtures of the 2,4- and 2,6-isomers. Two methods based o
22、n infrared spectroscopy are used to give accurate results over a broad range of isomer concentrations. Method A is applicable to toluenediisocyanate (TDI) samples containing between 5 % and 95 % of the 2,6-isomer. Method B is applicable to TDI samples containing 0 % to 5 % of the 2,6-isomer. Both me
23、thods are based on the quantitative measurement of absorption bands arising from out-of-plane CH deformation vibrations of the aromatic ring at 810 cm1and 782 cm1(12,3 m and 13,8 m).2 Normative referencesThe following documents are referred to in the text in such a way that some or all of their cont
24、ent constitutes requirements of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.ISO 648, Laboratory glassware Single-volume pipettesISO 4787, Laboratory glassware Volumetric
25、instruments Methods for testing of capacity and for useISO 6353-2, Reagents for chemical analysis Part 2: Specifications First series3 Terms and definitionsFor the purposes of this document, the following terms and definitions apply.ISO and IEC maintain terminological databases for use in standardiz
26、ation at the following addresses: IEC Electropedia: available at h t t p :/ www .electropedia .org/ ISO Online browsing platform: available at h t t p :/ www .iso .org/ obp3.1isomercompound having the same percentage composition and molecular mass as another compound, but differing in chemical struc
27、ture and properties3.2isomer contentamount of an isomer (3.1) expressed as a mass percentage of the total isomer amount3.3polyurethanepolymer prepared by the reaction of an organic di- or polyisocyanate with compounds containing two or more hydroxyl groups ISO 2017 All rights reserved 1BS ISO 15064:
28、2017ISO 15064:2017(E)4 SamplingSince organic isocyanates react with atmospheric moisture, take special precautions in sampling. Usual sampling methods (for example, sampling an open drum with a thief), even when conducted rapidly, can cause contamination of the sample with insoluble ureas; therefore
29、, blanket the sample with a dry inert gas (e.g. nitrogen, argon or dried air) at all times.WARNING Organic isocyanates are hazardous when absorbed through the skin or when the vapours are breathed in. Provide adequate ventilation and wear protective gloves and eyeglasses.5 Principle5.1 Method AIn me
30、thod A (between 5 % and 95 % 2,6-isomer), the infrared spectrum of a cyclohexane solution of the sample is recorded in the 770 cm1to 840 cm1(12 m to 13 m) region. The absorbance ratio of the 810 cm1and 782 cm1bands is measured and converted to % toluene-2,6-diisocyanate from a previously established
31、 calibration curve.5.2 Method BIn method B (0 % to 5 % 2,6-isomer), the absorbance of the 782 cm1band is measured from an infrared spectrum of an undiluted sample and then converted to % 2,6-isomer from a previously established calibration curve.6 ReagentsReagent-grade chemicals shall be used in all
32、 tests. Unless otherwise indicated, it is intended that the reagents shall conform to the specifications of ISO 6353-2. Other grades may be used, provided that it is first determined that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination
33、.6.1 Cyclohexane, distilled and stored over silica gel to remove traces of moisture.6.2 Diisocyanate standards.Pure samples of 2,4-TDI and 2,6-TDI are required for calibration. The following criteria can be used to judge purity:for 2,4-TDI: freezing point = 22,0 C; nD20= 1,567 81; 420= 1,218 6;for 2
34、,6-TDI: freezing point = 18,2 C; nD20= 1,571 11; 420= 1,227 0.The diisocyanates can be prepared by phosgenating the corresponding pure amines and vacuum-distilling the products. Since these diisocyanates will react with moisture and can discolour in the presence of air, store them under dry nitrogen
35、.NOTE Gas chromatography (GC) has also been used to establish purity. Isomers determined to be greater than 99,5 % pure by GC with either thermal conductivity (TCD) or flame ionization (FID) detection have been found suitable to be standards.2 ISO 2017 All rights reservedBS ISO 15064:2017ISO 15064:2
36、017(E)7 Apparatus7.1 Spectrophotometer. Any single- or double-beam recording infrared spectrophotometer, or FTIR spectrophotometer, accurate to 0,2 % transmission and capable of resolving the two peaks of the 2,4-isomer doublet at 810 cm1.7.2 Sealed sodium chloride (NaCl) liquid absorption cells, wi
37、th 0,2 mm (method A) and 0,1 mm (method B) path lengths. The actual path lengths of the cells shall be known to 0,002 mm.7.3 Glassware, 25 ml glass-stoppered volumetric flasks, 0,80 ml pipette and an all-glass syringe conforming to ISO 648 or ISO 4787.7.4 Laboratory balance, capable of weighing to 0
38、,1 mg.8 Test conditionsSince isocyanates react with moisture, keep laboratory humidity low, preferably under 50 % relative humidity. Thoroughly dry all laboratory ware. Store cells (7.2) in a dessicator and use thin rubber or plastic gloves while handling. Testing is done at room temperature (typica
39、lly 18 C to 27 C).9 Method A Samples containing between 5 % and 95 % of 2,6-TDI9.1 Calibration9.1.1 Weigh the amounts of pure 2,4- and 2,6-TDI given in Table 1, 2 or 3 as appropriate for the calibration range desired. Calibration over a narrow range gives more accurate results than a wide-range cali
40、bration.9.1.2 Prepare standard solutions and calibration curves as follows.9.1.2.1 Using a pipette, transfer 0,80 ml (0,98 g) of each standard isomer mixture into dry, 25 ml glass-stoppered volumetric flasks (7.3). Dilute each to volume with cyclohexane (6.1) and mix thoroughly.9.1.2.2 Fill two 0,2
41、mm sealed, liquid absorption cells (one for a single-beam instrument) with cyclohexane and record the spectrum from 770 cm1to 840 cm1(12 m to 13 m). Refill the sample cell with a solution from 9.1.2.1 and record the spectrum, superimposing it over the previously recorded solvent spectrum. Repeat the
42、 process for each solution in 9.1.2.1.9.1.2.3 Using the solvent spectrum as the baseline, measure the absorbance of each standard solution at 810 cm1(2,4-TDI) and 782 cm1(2,6-TDI) and calculate the 810/782 cm1absorbance ratio. See Figure A.4 for an illustrative spectrum. Construct a calibration curv
43、e (see Figure A.1) by plotting absorbance ratio (ordinate) versus mass ratio of 2,4- to 2,6-TDI (abscissa).9.1.2.4 For convenience in narrow-range calibrations, the absorbance ratio may be plotted against the concentration (expressed in mass %) of each isomer (see Figure A.2 and Figure A.3). This al
44、lows direct ISO 2017 All rights reserved 3BS ISO 15064:2017ISO 15064:2017(E)determination of composition without equations. However, the relationship is not linear and the shape of the calibration curve shall be carefully determined.Table 1 Approximate standard mixtures for wide-range 2,4-/2,6-TDI c
45、alibrationMass ratio% 2,4-TDI % 2,6-TDI 2,4/2,6-TDI5,0 95,0 0,0510,0 90,0 0,1120,0 80,0 0,2530,0 70,0 0,4340,0 60,0 0,6750,0 50,0 1,0060,0 40,0 1,5070,0 30,0 2,3380,0 20,0 4,0090,0 10,0 9,0095,0 5,0 19,00Table 2 Approximate standard mixtures for 80 % 2,4-/20 % 2,6-TDI samplesMass ratio% 2,4-TDI % 2,
46、6-TDI 2,4/2,6-TDI75,0 25,0 3,0078,5 21,5 3,6579,0 21,0 3,7679,5 20,5 3,8880,0 20,0 4,0080,5 19,5 4,1381,0 19,0 4,2681,5 18,5 4,4085,0 15,0 5,67Table 3 Approximate standard mixtures for 65 % 2,4-/35 % 2,6-TDI samplesMass ratio% 2,4-TDI % 2,6-TDI 2,4/2,6-TDI60,0 40,0 1,5063,5 36,5 1,7464,0 36,0 1,7764
47、,5 35,5 1,8265,0 35,0 1,8665,5 34,5 1,9066,0 34,0 1,9466,5 33,5 1,9870,0 30,0 2,334 ISO 2017 All rights reservedBS ISO 15064:2017ISO 15064:2017(E)9.2 ProcedureUsing a pipette (7.3), transfer 0,80 ml (0,98 g) of sample into a dry, glass-stoppered volumetric flask (7.3). Dilute to volume with cyclohex
48、ane (6.1) and mix thoroughly. Fill a 0,2 mm cell with the solution and record the spectrum from 770 cm1to 840 cm1(12 m to 13 m) and, without changing the instrument settings, refill the sample cell with pure solvent and record its spectrum superimposed on the sample spectrum.9.3 Expression of result
49、s9.3.1 Using the solvent spectrum as the baseline, measure the absorbance of the sample at 810 cm1(2,4-TDI) and 782 cm1(2,6-TDI) and calculate the 810/782 cm1absorbance ratio. Read from the appropriate calibration curve the isomer mass ratio (Figure A.1) or percentage composition (Figures A.2 and A.3) that corresponds to the measured absorbance ratio.9.3.2 When using the isomer mass ratio, calculate the percentage of each isomer using Formula (1) and Formu
