1、BRITISH STANDARD BS EN ISO 3001:1999 Plastics Epoxycompounds Determination of epoxy equivalent The European Standard EN ISO 3001:1999 has the status of a British Standard ICS 83.080.01BSENISO3001:1999 This British Standard, having been prepared under the directionof the Sector Committeefor Materials
2、 and Chemicals, was published underthe authority of the Standards Committee and comesinto effect on 15 May 1999 BSI 02-2000 ISBN 0 580 32302 1 National foreword This British Standard is the English language version of EN ISO 3001:1999. Itis identical with ISO 3001:1999. It supersedes BS 2782-4:Metho
3、ds 433C and433D:1997 which is withdrawn. The UK participation in its preparation was entrusted to Technical Committee PRI/42, Fibre reinforced thermosetting plastics and prepregs, which has the responsibility to: aid enquirers to understand the text; present to the responsible international/European
4、 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 committee can be obtained on request to its secretary. Cross
5、-references Attention is drawn to the fact that CEN and CENELEC Standards normally include an annex which lists normative references to international publications with their corresponding European publications. The British Standards which implement these international or European publications may be
6、 found in the BSI Standards Catalogue under the section entitled “International Standards Correspondence 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 Stan
7、dards are responsible for their correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. Summary of pages This document comprises a front cover, an inside front cover, pagesi andii, theEN ISO title page, page 2, the ISO title page, pages ii t
8、o iv, pages1 to4, aninside back cover and a back cover. This standard has been updated (see copyright date) and may have had amendments incorporated. This will be indicated in the amendment table on the inside front cover. Amendments issued since publication Amd. No. Date CommentsBSENISO3001:1999 BS
9、I 02-2000 i Contents Page National foreword Inside front cover Foreword 2 Foreword iii Text of ISO 3001 1ii blankEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM ENISO 3001 February1999 ICS 83.080.00 English version Plastics Epoxy compounds Determination of epoxy equivalent (ISO 3001:1999) Plastiqu
10、es Compositions poxydiques Dtermination de lquivalent poxy (ISO3001:1999) Kunststoffe Epoxid-Verbindungen Bestimmung des Epoxid-quivalents (ISO3001:1999) This European Standard was approved by CEN on 25 January 1999. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which sti
11、pulate 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. This European Standard
12、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 are the national standards
13、 bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom. CEN European Committee for Standardization Comit Europen de Normalisation Europisches Komitee fr
14、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 ISO 3001:1999 EENISO3001:1999 BSI 02-2000 2 Foreword The text of the International Standard ISO3001:1999 has been
15、 prepared by Technical Committee ISO/TC 61 “Plastics” in collaboration with Technical Committee CEN/TC 249 “Plastics”, the secretariat of which is held by IBN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at th
16、e latest by August 1999, and conflicting national standards shall be withdrawn at the latest by August 1999. 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 Repub
17、lic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of the International Standard ISO3001:1999 was approved by CEN as a European Standard without any modific
18、ation.ENISO3001:1999 ii BSI 02-2000 Contents Page Foreword iii 1 Scope 1 2 Definitions 1 3 Principle 1 4 Reagents 1 5 Apparatus 2 6 Procedure 2 7 Expression of results 3 8 Precision 3 9 Test report 4 Annex A (normative) Modification applicable to epoxyamines Inside back coverENISO3001:1999 BSI 02-20
19、00 iii 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 wh
20、ich 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
21、matters of electrotechnical standardization. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. International Standard ISO 3
22、001 was prepared by Technical Committee ISO/TC 61, Plastics, Subcommittee SC 12, Thermosetting materials. This fourth edition cancels and replaces the third edition (ISO 3001:1997), which has been technically revised. Annex A forms an integral part of this International Standard.iv blankENISO3001:19
23、99 BSI 02-2000 1 1 Scope This International Standard specifies a method for the determination of the epoxy equivalent and is applicable to all epoxy compounds. In the case of epoxyamines, it is necessary to apply the modification specified in Annex A. 2 Definitions For the purposes of this Internati
24、onal Standard, the following definitions apply. 2.1 epoxy equivalent the mass of resin, in grams, which contains one mole of epoxy groups 2.2 epoxy index the number of moles of epoxy groups contained in1kg of resin 3 Principle The epoxy groups in a test portion are reacted with nascent hydrogen brom
25、ide produced by the action of0,1mol/l standard volumetric perchloric acid solution on tetraethylammonium bromide. The end-point is determined either using crystal violet as indicator or by a potentiometric method. 4 Reagents During the analysis, use only reagents of recognized analytical grade. 4.1
26、Glacial acetic acid 4.2 Acetic anhydride, purity 96 %. 4.3 Chloroform 4.4 Potassium hydrogen phthalate 4.5 Crystal violet, indicator solution. Dissolve 100 mg of crystal violet in 100 ml of glacial acetic acid (4.1). 4.6 Perchloric acid, 0,1 mol/l standard volumetric solution. 4.6.1 Preparation Add
27、8,5 ml of a 70 % (m/m) aqueous solution of perchloric acid to a solution consisting of a mixture of 500ml of glacial acetic acid (4.1) and 30 ml of acetic anhydride (4.2). Make up to 1 000 ml with glacial acetic acid and mix thoroughly. 4.6.2 Standardization WARNING The use of safety goggles and a s
28、afety screen is recommended. Standardize this solution by titrating it against200mg of potassium hydrogen phthalate(4.4) previously dried, if necessary, for2 h at 120 C dissolved in 20 ml of glacial acetic acid (4.1) and10ml of chloroform (4.3), using crystal violet indicator solution (4.5) or a pot
29、entiometric titration apparatus (5.1). Carry out the end-point determination using 4 to6drops of crystal violet solution, titrating until a stable green colour is obtained, or carry out this procedure using a potentiometric titration apparatus. If a potentiometric method is used to determine the epo
30、xy equivalent, it is necessary to use the same method for the standardization of the perchloric acid. Note the temperature t sof the standard volumetric solution.ENISO3001:1999 2 BSI 02-2000 4.6.3 Calculation of the concentration Calculate the concentration c of the perchloric acid solution (4.6.1),
31、 in moles per litre, by the following equation, rounding to four places of decimals: where 4.7 Tetraethylammonium bromide, reagent solution. Dissolve 100 g of tetraethylammonium bromide in400 ml of glacial acetic acid (4.1). Add a few drops of crystal violet solution (4.5). If it changes colour, bri
32、ng it back to the original (blue-green) colour with standard volumetric perchloric acid solution (4.6). For some epoxy compounds of low reactivity, the use of tetrabutylammonium iodide is advised, either as the solid or as a 10 % solution in chloroform. In this case, light shall be excluded as much
33、as possible. Solutions of tetrabutylammonium iodide in chloroform are unstable and shall be freshly prepared for each titration. 5 Apparatus 5.1 Potentiometric titration apparatus, equipped with a silver electrode and a silver chloride or mercury sulfate electrode. 5.2 Balance, accurate to within 0,
34、1 mg. 5.3 Conical flask, capacity 100 ml or 200 ml, with ground-glass neck and ground-glass stopper. 5.4 Microburette, with closed reservoir, or calibrated burette, capacity 10 ml. 5.5 Glass apparatus, with ground joints, vents being protected from moisture by calcium chloride tubes. 5.6 Magnetic st
35、irrer, with polytetrafluoroethylene-coated bar. 5.7 Thermometer, calibrated to permit temperature measurements to within 0,1 C. 5.8 Pipette, capacity 10 ml. 5.9 Volumetric flask, capacity 1 000 ml. 5.10 Measuring cylinders, capacity 50 ml and500ml. 6 Procedure 6.1 Weigh into the flask, to the neares
36、t 0,1 mg, a testportion containing 0,6 mmol to 0,9 mmol of epoxy groups (this corresponds to a mass of between0,6 EE mg and 0,9 EE mg, where EE is the estimated epoxy equivalent). 6.2 Add 10 ml of chloroform (4.3), then dissolve the test portion using the magnetic stirrer (5.6) and, if necessary, by
37、 heating slightly. Cool to room temperature, add 20 ml of glacial acetic acid (4.1) and then, with the pipette (5.8), 10 ml of tetraethylammonium bromide solution (4.7). In the case of high-molecular-mass epoxy resins, increase the chloroform volume to 30 ml. 6.3 If using the indicator method, add 4
38、 to 6 drops of crystal violet solution (4.5) and titrate the solution on the magnetic stirrer with perchloric acid solution(4.6). Carry out the titration until a stable green colour is obtained. 6.4 If using the potentiometric method, place the electrodes in the test solution. Adjust the speed of th
39、e magnetic stirrer to give vigourous stirring without splattering. Titrate the solution with perchloric acid solution (4.6). 6.5 Note the temperature t of the perchloric acid solution in order to be able to allow for expansion of the solution with increasing temperature. m is the mass, in grams, of
40、potassium hydrogen phthalate used; V o is the volume, in millilitres, of perchloric acid solution (4.6.1) used in the blank test; V 1 is the volume, in millilitres, of perchloric acid solution (4.6.1) used in the determination.ENISO3001:1999 BSI 02-2000 3 6.6 Carry out a blank test at the same time
41、as the determination, following the same procedure and using the same reagents but omitting the test portion. 7 Expression of results Calculate the epoxy equivalent EE, in grams per mole, by the following equation, rounding to three places of decimals: where NOTEThe use of the correction factor is n
42、ecessary because of the significant coefficient of expansion of the perchloric acid solution(1,07 10 3 C 1 ), which corresponds to a volume variation of 0,1 % per degree Celsius. Use of this factor can be avoided by working in a temperature-controlled room. The result is sometimes expressed as the e
43、poxy index, expressed in moles of epoxy groups per kilogram, calculated as follows: 8 Precision The precision of this method was determined in accordance with ISO 5725, Accuracy (trueness and precision) of test methods and results, following round-robin testing organized in Japan in 1996. The repeat
44、ability and reproducibility values for liquid and solid bisphenol A type epoxy resins are as follows: Liquid bisphenol A type epoxy resins Solid bisphenol A type epoxy resins where m is the mass, in grams, of the test portion; V 0 is the volume, in millilitres, of perchloric acid solution (4.6) used
45、 in the blank test; V 1 is the volume, in millilitres, of perchloric acid solution (4.6) used in the determination; t is the temperature, in degrees Celsius, of the perchloric acid solution (4.6) at the time of the determination and blank test; t s is the temperature, in degrees Celsius, of the perc
46、hloric acid solution (4.6) at the time of standardization; c is the concentration, in moles per litre, of the perchloric acid solution (4.6) (usually0,1mol/l) at the time of standardization. Titration method Repeatability Reproducibility Average value of EE s r r s R R Potentiometric 0,61 1,72 1,22
47、3,41 187,0 Indicator 0,68 1,91 1,04 2,91 188,2 Titration method Repeatability Reproducibility Average value of EE s r r s R R Potentiometric 0,87 2,43 6,68 18,71 916,3 Indicator 2,94 8,24 8,01 22,44 919,2 s r is the within-laboratory standard deviation; r is the repeatability (absolute value); s R i
48、s the between-laboratory standard deviation; R is the reproducibility (absolute value).ENISO3001:1999 4 BSI 02-2000 9 Test report The test report shall include the following particulars: a) a reference to this International Standard; b) all details necessary for complete identification of the sample
49、; c) the reagent used, if not tetraethylammonium bromide; d) the result of the test and the way in which it is expressed; e) details of any operation not included in this International Standard as well as details of any incident likely to have affected the result; f) the date of the test.ENISO3001:1999 BSI 02-2000 Annex A (normative) Modification applicable to epoxyamines A.1 Scope When determinations are carried out on nitrogen-containing epoxy resins (i.e. epoxyamines) using the method described in the body of this I
