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1、 Reference number ISO 15064:2004(E) ISO 2004 INTERNATIONAL STANDARD ISO 15064 First edition 2004-08-15 Plastics Aromatic isocyanates for use in the production of polyurethanes Determination of the isomer ratio in toluenediisocyanate Plastiques Isocyanates aromatiques pour utilisation dans la product
2、ion de polyurthannes Dtermination du rapport des isomres dans le diisocyanate de tolune Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/20/2007 03:43:19 MDTNo reproduction or networking
3、permitted without license from IHS -,-,- ISO 15064:2004(E) PDF disclaimer This PDF file may contain embedded typefaces. In accordance with Adobes licensing policy, this file may be printed or viewed but shall not be edited unless the typefaces which are embedded are licensed to and installed on the
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6、 the Central Secretariat at the address given below. ISO 2004 All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying and microfilm, without permission in writing from eit
7、her ISO at the address below or ISOs member body in the country of the requester. ISO copyright office Case postale 56 CH-1211 Geneva 20 Tel. + 41 22 749 01 11 Fax + 41 22 749 09 47 E-mail copyrightiso.org Web www.iso.org Published in Switzerland ii ISO 2004 All rights reserved Copyright Internation
8、al Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/20/2007 03:43:19 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 15064:2004(E) ISO 2004 All rights reserved iii Contents Page For
9、ewordiv Introduction v 1 Scope1 2 Normative references .1 3 Terms and definitions.1 4 Sampling2 5 Principle.2 6 Reagents2 7 Apparatus.3 8 Test conditions3 9 Method A Samples containing 5 % to 95 % of 2,6-TDI3 10 Method B Samples containing 0 % to 5 % of 2,6-TDI6 Annex A (normative) Calibration curve
10、s8 Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/20/2007 03:43:19 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 15064:2004(E) iv ISO 2004 All rights res
11、erved Foreword ISO (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 for whi
12、ch 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 all m
13、atters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted by the technical committees are cir
14、culated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. 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 respon
15、sible for identifying any or all such patent rights. ISO 15064 was prepared by Technical Committee ISO/TC 61, Plastics, Subcommittee SC 12, Thermosetting materials. Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/997
16、2545001 Not for Resale, 04/20/2007 03:43:19 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 15064:2004(E) ISO 2004 All rights reserved v Introduction No International Standard for the determination of isomer contents of toluenediisocyanate (TDI) has been published. This
17、 International Standard is based on infrared spectroscopy and consists of two test methods that can be used to determine the 2,4- and 2,6-isomer contents of commercially important toluenediisocyanates over a broad range of isomer concentrations. It is important to know the isomer content of TDI sinc
18、e the isomers have different reaction rates, and the processing and properties of polyurethane systems, especially flexible polyurethane foams, may be significantly affected. This method is based on work done in the Bayer Central Analytical Department (Leverkusen) in the early 1960s, and was origina
19、lly published as part of ASTM D 1638. It is now designated ASTM D 4660, Standard Test Methods for Polyurethane Raw Materials: Determination of the Isomer Content of Toluenediisocyanate. Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Tech
20、nical Standards 1/9972545001 Not for Resale, 04/20/2007 03:43:19 MDTNo reproduction or networking permitted without license from IHS -,-,- Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04
21、/20/2007 03:43:19 MDTNo reproduction or networking permitted without license from IHS -,-,- INTERNATIONAL STANDARD ISO 15064:2004(E) ISO 2004 All rights reserved 1 Plastics Aromatic isocyanates for use in the production of polyurethanes Determination of the isomer ratio in toluenediisocyanate WARNIN
22、G Persons using this International Standard should be familiar with normal laboratory practice. This standard does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health prac
23、tices and to ensure compliance with any national regulatory conditions prior to use. 1 Scope This International Standard specifies methods for the measurement of toluene-2,6-diisocyanate in mixtures of the 2,4- and 2,6-isomers. Two methods based on infrared spectroscopy are required to give accurate
24、 results over a broad range of isomer concentrations. Method A is applicable to TDI samples containing 5 % to 95 % of the 2,6-isomer. Method B is applicable to TDI samples containing 0 % to 5 % of the 2,6-isomer. Both methods are based on the quantitative measurement of absorption bands arising from
25、 out-of-plane CH deformation vibrations of the aromatic ring at 810 cm1 and 782 cm1 (12,3 m and 13,8 m). 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the
26、 latest edition of the referenced document (including any amendments) applies. ISO 648, Laboratory glassware One-mark pipettes ISO 4787, Laboratory glassware Volumetric glassware Methods for use and testing of capacity ISO 6353-2, Reagents for chemical analysis Part 2: Specifications First series 3
27、Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 isomer a compound having the same percentage composition and molecular mass as another compound, but differing in chemical structure and properties 3.2 isomer content the amount of an isomer expre
28、ssed as a mass percentage of the total isomer amount Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/20/2007 03:43:19 MDTNo reproduction or networking permitted without license from IHS
29、-,-,- ISO 15064:2004(E) 2 ISO 2004 All rights reserved 3.3 TDI toluenediisocyanate 3.4 polyurethane a polymer prepared by the reaction of an organic di- or polyisocyanate with compounds containing two or more hydroxyl groups 4 Sampling Since organic isocyanates react with atmospheric moisture, take
30、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, blanket the sample with a dry inert gas (e.g. nitrogen, argon or dried air) at all times. WAR
31、NING 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 Principle 5.1 Method A In method A (5 % to 95 % 2,6-isomer), the infrared spectrum of a cyclohexane solution of the sa
32、mple is recorded in the 770 cm1 to 840 cm1 (12 m to 13 m) region. The absorbance ratio of the 810 cm1 and 782 cm1 bands is measured and converted to % toluene-2,6-diisocyanate from a previously established calibration curve. 5.2 Method B In Method B (0 % to 5 % 2,6-isomer), the absorbance of the 782
33、 cm1 band is measured from an infrared spectrum of an undiluted sample and then converted to % 2,6-isomer from a previously established calibration curve. 6 Reagents Reagent-grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that the reagents shall conform to the
34、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. 6.1 Cyclohexane, distilled and stored over silica gel to remove traces of moisture. 6.2
35、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; 20 D n = 1,567 81; 20 4 = 1,218 6 for 2,6-TDI: freezing point = 18,2 C; 20 D n = 1,571 11; 20 4 = 1,227 0. The diisocyan
36、ates can be prepared by phosgenating the corresponding pure amines and vacuum-distilling the products. Since these diisocyanates will react with moisture and may discolour in the presence of air, store them under dry nitrogen. Copyright International Organization for Standardization Provided by IHS
37、under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/20/2007 03:43:19 MDTNo reproduction or networking permitted without license from IHS -,-,- ISO 15064:2004(E) ISO 2004 All rights reserved 3 7 Apparatus 7.1 Spectrophotometer: any single- or double-beam recording
38、 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, with 0,2 mm (method A) and 0,1 mm (method B) path lengths. The actual path le
39、ngths 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 0,1 mg. 8 Test conditions Since isocyanates react with moisture, keep labo
40、ratory 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 handing. 9 Method A Samples containing 5 % to 95 % of 2,6-TDI 9.1 Calibration 9.1.1 Weigh the amounts of pure 2,4- and 2,6-T
41、DI 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 calibration. 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 stan
42、dard isomer mixture into dry, 25 ml glass- stoppered volumetric flasks (see 7.3). Dilute each to volume with cyclohexane (6.1) and mix thoroughly. 9.1.2.2 Fill two 0,2 mm sealed, liquid absorption cells (one for a single-beam instrument) with cyclohexane and record the spectrum from 770 cm1 to 840 c
43、m1 (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 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
44、 solution at 810 cm1 (2,4-TDI) and 782 cm1 (2,6-TDI) and calculate the 810/782 cm1 absorbance ratio. See Figure A.4 in Annex A for an illustrative spectrum. Construct a calibration curve (see Figure A.1) by plotting absorbance ratio (ordinate) versus mass ratio of 2,4- to 2,6-TDI (abscissa). 9.1.2.4
45、 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 allows direct determination of composition without equations. However, the relationship is not linear and the shape
46、of the calibration curve must be carefully determined. Copyright International Organization for Standardization Provided by IHS under license with ISO Licensee=NASA Technical Standards 1/9972545001 Not for Resale, 04/20/2007 03:43:19 MDTNo reproduction or networking permitted without license from IH
47、S -,-,- ISO 15064:2004(E) 4 ISO 2004 All rights reserved Table 1 Approximate standard mixtures for wide-range 2,4-/2,6-TDI calibration Mass ratio % 2,4-TDI % 2,6-TDI 2,4-/2,6-TDI 5,0 95,0 0,05 10,0 90,0 0,11 20,0 80,0 0,25 30,0 70,0 0,43 40,0 60,0 0,67 50,0 50,0 1,00 60,0 40,0 1,50 70,0 30,0 2,33 80
48、,0 20,0 4,00 90,0 10,0 9,00 95,0 5,0 19,00 Table 2 Approximate standard mixtures for 80 % 2,6-/20 % 2,4-TDI samples Mass ratio % 2,4-TDI % 2,6-TDI 2,4-/2,6-TDI 75,0 25,0 3,00 78,5 21,5 3,65 79,0 21,0 3,76 79,5 20,5 3,88 80,0 20,0 4,00 80,5 19,5 4,13 81,0 19,0 4,26 81,5 18,5 4,40 85,0 15,0 5,67 Table 3 Approximate standard mixtures for 65 % 2,6-/35 % 2,4-TDI samples Mass ratio % 2,4-TDI