1、BSI Standards PublicationBS ISO 11235:2016Rubber compoundingingredients Sulfenamideaccelerators Test methodsBS ISO 11235:2016 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 11235:2016. It supersedes BS ISO 11235:1999 which is withdrawn. The UK participation in
2、 its preparation was entrusted to Technical Committee PRI/50, Raw materials (including latex) for use in the rubber industry.A list 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
3、a contract. Users are responsible for its correct application. The British Standards Institution 2016.Published by BSI Standards Limited 2016ISBN 978 0 580 89098 7 ICS 83.040.20 Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under
4、 the authority of the Standards Policy and Strategy Committee on 31 January 2016.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e dBS ISO 11235:2016 ISO 2016Rubber compounding ingredients Sulfenamide accelerators Test methodsIngrdients de mlange du caoutchouc Acclrateurs de t
5、ype sulfnamide Mthodes dessaiINTERNATIONAL STANDARDISO11235Second edition2016-01-15Reference numberISO 11235:2016(E)BS ISO 11235:2016ISO 11235:2016(E)ii ISO 2016 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2016, Published in SwitzerlandAll rights reserved. Unless otherwise specified, no part
6、 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 ISOs member bod
7、y 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 11235:2016ISO 11235:2016(E)Foreword v1 Scope . 12 Normative references 13 Terms and definitions . 24 Determin
8、ation of physical and chemical properties. 24.1 Sampling . 24.2 Test methods . 24.3 Limit of acceptance . 25 Test methods for purity . 35.1 Method to determine purity by reduction with MBT and titration . 35.1.1 Scope 35.1.2 Principle 35.1.3 Reagents 35.1.4 Apparatus . 45.1.5 Procedure . 45.1.6 Expr
9、ession of results (methods A and B) . 55.2 Method to determine purity by high performance liquid chromatography (HPLC) 65.2.1 Scope 65.2.2 Principle 75.2.3 Significance and use 75.2.4 Interferences . 75.2.5 Reagents and materials 75.2.6 Apparatus . 75.2.7 Calibration and standardization . 85.2.8 Pro
10、cedure . 85.2.9 Sample analysis . 95.2.10 Expression of results 95.3 Precision 106 Test method for insoluble material .106.1 Scope . 106.2 Principle . 106.3 Significance and use 106.4 Reagents. 106.5 Apparatus . 116.6 Procedure . 116.7 Expression of results . 127 Test methods for melting range .127.
11、1 Melting range by capillary tube . 127.1.1 Scope . 127.1.2 Significance and use .127.1.3 Limitations . 127.1.4 Apparatus 127.1.5 Preparation of test sample . 137.1.6 Procedure 137.2 Melting range by differential scanning calorimetry (DSC) 137.2.1 Scope . 137.2.2 Significance and use .147.2.3 Limita
12、tions . 147.2.4 Apparatus 147.2.5 Preparation of test sample . 147.2.6 Procedure 148 Test method for volatile material 15 ISO 2016 All rights reserved iiiContents PageBS ISO 11235:2016ISO 11235:2016(E)8.1 Scope . 158.2 Principle . 158.3 Apparatus . 158.4 Procedure . 158.5 Expression of results . 169
13、 Test method for wet sieve analysis .169.1 Scope . 169.2 Significance and use 169.3 Materials 169.4 Apparatus . 169.5 Procedure . 179.6 Expression of results . 1710 Test method for the determination of ash 1710.1 Scope . 1710.2 Principle . 1810.3 Significance and use 1810.4 Apparatus . 1810.5 Proced
14、ure . 1810.6 Expression of results . 1911 Test report 19Annex A (normative) Classification and key properties of sulfenamide (class 1) vulcanization accelerators 20Annex B (informative) Precision 23Bibliography .25iv ISO 2016 All rights reservedBS ISO 11235:2016ISO 11235:2016(E)ForewordISO (the Inte
15、rnational 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 which a technical committee has
16、 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 matters of electrotechnical s
17、tandardization.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. This document was drafted in acco
18、rdance 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 any or all such patent rights. Detail
19、s 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 of users and does not constitute an endo
20、rsement.For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT), see the following URL: Foreword Supplementary information .The committee respo
21、nsible for this document is ISO/TC 45, Rubber and rubber products, Subcommittee SC 3, Raw materials (including latex) for use in the rubber industry.This second edition cancels and replaces the first edition (ISO 11235:1999), which have been technically revised: the method to determine purity by hig
22、h performance liquid chromatography (HPLC) is stated as the preferred method in the scope and in the new 5.2.1.3; the normative references in Clause 2 and in the text have been updated; precision data in 4.2.12 have been moved in an informative Annex B and a Bibliography has been added. ISO 2016 All
23、 rights reserved vBS ISO 11235:2016BS ISO 11235:2016Rubber compounding ingredients Sulfenamide accelerators Test methodsWARNING Persons using this International Standard should be familiar with normal laboratory practice. This International Standard does not purport to address all of the safety prob
24、lems, if any, associated with its use. It is the responsibility of the user to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions.1 ScopeThis International Standard specifies the methods to be used for the evaluation of sulfenamide acce
25、lerators: MBTS: benzothiazyl disulphide; CBS: N-cyclohexylbenzothiazole-2-sulfenamide; TBBS: N-tert-butylbenzothiazole-2-sulfenamide; DIBS: N,N-diisopropylbenzothiazole-2-sulfenamide; DCBS: N,N-dicyclohexylbenzothiazole-2-sulfenamide; MBS: N-oxydiethylenebenzothiazole-2-sulfenamide.NOTE Although MBT
26、S is not a sulfenamide, it is the primary decomposition product of these accelerators and quantitatively determined by the method specified in 5.2.The analytical methods are applicable for most commercial sulfenamide accelerators: sulfenamides of primary amines (type I); sulfenamides of unhindered s
27、econdary amines (type II); sulfenamides of hindered secondary amines (type III).The method (5.2) to determine purity by high performance liquid chromatography (HPLC) is the preferred method.2 Normative referencesThe following documents, in whole or in part, are normatively referenced in this documen
28、t and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.ISO 385, Laboratory glassware BurettesISO 648, Laboratory glassware Single-volume pipettesISO 17
29、72, Laboratory crucibles in porcelain and silicaISO 3819, Laboratory glassware BeakersISO 4788, Laboratory glassware Graduated measuring cylindersISO 4793, Laboratory sintered (fritted) filters Porosity grading, classification and designationISO 6556, Laboratory glassware Filter flasksINTERNATIONAL
30、STANDARD ISO 11235:2016(E) ISO 2016 All rights reserved 1BS ISO 11235:2016ISO 11235:2016(E)ISO 15528, Paints, varnishes and raw materials for paints and varnishes Sampling3 Terms and definitionsFor the purposes of this document, the following terms and definitions apply.3.1external standard calculat
31、ionmethod of calculating the analyte content by measuring the area of the analyte peak, multiplying it by a response factor, and dividing it by the sample concentrationNote 1 to entry: All components are assumed to be resolved from the component of interest.3.2lot samplesample from production repres
32、entative of a standard production unit, normally referred to as “the sample”3.3test portionactual material, representative of the lot sample, used for a particular determination4 Determination of physical and chemical properties4.1 SamplingThe sampling of the product shall be performed in accordance
33、 with ISO 15528.To ensure homogeneity, thoroughly blend at least 250 g of the lot sample before removing the test portion.4.2 Test methodsTable 1 List of the test methodsProperty Clause or subclause of this International StandardPurity by reduction with MBT and titration 5.1Purity by high performanc
34、e liquid chromatography (HPLC) 5.2Insoluble material 6Melting range by capillary tube 7.1Melting range by differential scanning calorimetry (DSC) 7.2Volatile material 8Wet sieve analysis 9Ash 104.3 Limit of acceptanceThe difference between the results of duplicate determinations shall not exceed the
35、 repeatability of the test, if it is defined. Otherwise, it is necessary to repeat the test. When the repeatability is not defined, the results of both determinations shall be reported.2 ISO 2016 All rights reservedBS ISO 11235:2016ISO 11235:2016(E)5 Test methods for purity5.1 Method to determine pu
36、rity by reduction with MBT and titration5.1.1 ScopeThe following method is suitable for determining the purity and free amine in sulfenamides commonly used in the rubber industry and is applicable to CBS, DCBS, MBS and TBBS.5.1.2 PrincipleAfter neutralization of the free amine, the sulfenamide is re
37、duced by means of a solution of mercaptobenzothiazole (MBT). An excess of hydrochloric acid is added and the unreacted hydrochloric acid is then titrated with sodium hydroxide using one of the two following methods: method A: potentiometric titration; method B: titration using an indicator.5.1.3 Rea
38、gentsDuring the analysis, use only reagents of recognized analytical grade and only distilled water or water of equivalent purity.5.1.3.1 Basic reagents for methods A and B5.1.3.1.1 Mercaptobenzothiazole (MBT), min. assay 99,0 %.5.1.3.1.2 Absolute ethanol.5.1.3.1.3 Toluene.5.1.3.1.4 Hydrochloric aci
39、d, standard volumetric solution, c(HCl) = 0,1 mol/dm3.5.1.3.1.5 Hydrochloric acid, standard volumetric solution, c(HCl) = 0,5 mol/dm3.5.1.3.1.6 Sodium hydroxide, standard volumetric solution, c(NaOH) = 0,1 mol/dm3, carbonate free.5.1.3.1.7 Sodium hydroxide, standard volumetric solution, c(NaOH) = 0,
40、5 mol/dm3, carbonate free.5.1.3.1.8 Bromophenol blue, 10 g/dm3solution.Dissolve 1 g of bromophenol blue with a small volume of ethanol (5.1.3.1.2). Transfer to a 100 cm3volumetric flask and neutralize with the sodium hydroxide solution (5.1.3.1.6) to a green colour. Dilute to the mark with ethanol (
41、5.1.3.1.2).5.1.3.2 Prepared reagent for method A5.1.3.2.1 Mercaptobenzothiazole, 40 g/dm3solution, freshly prepared.Weigh a suitable quantity of MBT (5.1.3.1.1) to the nearest 0,1 g and dissolve in absolute ethanol (5.1.3.1.2). If the MBT does not dissolve completely, heat the solution to a temperat
42、ure no higher than (55 2) C (not exceeding 57 C) to ensure complete dissolution. Cool to room temperature and dilute to the mark of a suitable volumetric flask with absolute ethanol. ISO 2016 All rights reserved 3BS ISO 11235:2016ISO 11235:2016(E)5.1.3.3 Prepared reagent for method B5.1.3.3.1 Ethano
43、l (5.1.3.1.2)/toluene (5.1.3.1.3) solution, 5:3 (V:V)5.1.3.3.2 Mercaptobenzothiazole, 40 g/dm3solution, freshly prepared.Weigh a suitable quantity of MBT (5.1.3.1.1) to the nearest 0,1 g and dissolve in the ethanol/toluene solution (5.1.3.3.1). If the MBT does not dissolve completely, heat the solut
44、ion to a temperature no higher than (55 2) C (not exceeding 57 C) to ensure complete dissolution. Cool to room temperature and dilute to the mark of a suitable volumetric flask with the ethanol/toluene solution (5.1.3.3.1).5.1.4 Apparatus5.1.4.1 Mortar and pestle or other appropriate grinding device
45、.5.1.4.2 Pipette, 25 cm3capacity, in accordance with the specifications given in ISO 648.5.1.4.3 Burette, 25 cm3capacity, graduated in 0,05 cm3, in accordance with the general specifications given in ISO 385.5.1.4.4 Beaker, 250 cm3capacity, in accordance with the specifications given in ISO 3819.5.1
46、.4.5 Temperature-controlled bath, capable of being maintained at (55 2) C.5.1.4.6 Stop-watch.5.1.4.7 Magnetic stirrer.5.1.4.8 pH-meter, with a resolution of 0,1 unit or better.5.1.4.9 Analytical balance, accurate to within 0,1 mg.5.1.5 Procedure5.1.5.1 Method A5.1.5.1.1 Grind a sample and weigh a te
47、st portion of approximately 2 g of the blended powder to the nearest 0,1 mg. For TBBS, weigh approximately 1,6 g of the test sample. Transfer it to the beaker (5.1.4.4).5.1.5.1.2 Add 50 cm3of ethanol (5.1.3.1.2) and stir until dissolved. If needed, heat the solution to a temperature no higher than 5
48、5 C. A slight turbidity may remain.5.1.5.1.3 Cool to room temperature. Add 3 drops of indicator (5.1.3.1.8) and titrate the free amine with 0,1 mol/dm3hydrochloric acid (5.1.3.1.4) to the blue-green-colour end point (V1).5.1.5.1.4 Add 50 cm3of the MBT solution (5.1.3.2.1) and immediately pipette 25
49、cm3of 0,5 mol/dm3hydrochloric acid (5.1.3.1.5), exactly measured.5.1.5.1.5 Stir the solution in a temperature-controlled bath (5.1.4.5) maintained at (55 2) C for exactly 5 min, timed with the stop-watch (5.1.4.6).4 ISO 2016 All rights reservedBS ISO 11235:2016ISO 11235:2016(E)5.1.5.1.6 Titrate potentiometrically the unreacted hydrochloric acid with the 0,5 mol/dm3sodium hydroxide (5.1.3.1.7). With continued stirring, add the sodium hydroxide stepwise in increments of 1 cm3, and reco
