1、Reference numberISO 11236:2000(E)ISO 2000INTERNATIONALSTANDARDISO11236First edition2000-03-15Rubber compounding ingredients p-Phenylenediamine (PPD)antidegradants Test methodsIngrdients de mlange du caoutchouc Antidgradantsdu type p-phnylnediamine (PPD) Mthodes dessaiCopyright International Organiza
2、tion for Standardization Provided by IHS under license with ISONot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO 11236:2000(E)PDF disclaimerThis PDF file may contain embedded typefaces. In accordance with Adobes licensing policy, this file may be printed or viewe
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7、www.iso.chPrinted in Switzerlandii ISO 2000 All rights reservedCopyright International Organization for Standardization Provided by IHS under license with ISONot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO 11236:2000(E) ISO 2000 All rights reserved iiiContents
8、PageForeword.iv1 Scope12 Normative references13 Terms and definitions .14 Abbreviations.25 Use and classification.26 Sampling and repeat determinations.37 Determination of purity by gas chromatography (GC)38 Determination of purity by high-performance liquid chromatography (HPLC).129 Determination o
9、f ash.1610 Determination of volatile matter.18Copyright International Organization for Standardization Provided by IHS under license with ISONot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO 11236:2000(E)iv ISO 2000 All rights reservedForewordISO (the Internation
10、al Organization for Standardization) is a worldwide federation of national standards bodies (ISOmember bodies). The work of preparing International Standards is normally carried out through ISO technicalcommittees. Each member body interested in a subject for which a technical committee has been est
11、ablished hasthe right to be represented on that committee. International organizations, governmental and non-governmental, inliaison with ISO, also take part in the work. ISO collaborates closely with the International ElectrotechnicalCommission (IEC) on all matters of electrotechnical standardizati
12、on.International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 3.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
13、the member bodies casting a vote.Attention is drawn to the possibility that some of the elements of this International Standard may be the subject ofpatent rights. ISO shall not be held responsible for identifying any or all such patent rights.International Standard ISO 11236 was prepared by Technic
14、al Committee ISO/TC 45, Rubber and rubber products,Subcommittee SC 3, Raw materials (including latex) for use in the rubber industry.Copyright International Organization for Standardization Provided by IHS under license with ISONot for ResaleNo reproduction or networking permitted without license fr
15、om IHS-,-,-INTERNATIONAL STANDARD ISO 11236:2000(E) ISO 2000 All rights reserved 1Rubber compounding ingredients p-Phenylenediamine (PPD)antidegradants Test methodsWARNING Persons using this International Standard should be familiar with normal laboratory practice.This standard does not purport to a
16、ddress all of the safety problems, if any, associated with its use. It isthe responsibility of the user to establish appropriate safety and health practices and to ensure compliancewith any national regulatory conditions.1 ScopeThis International Standard applies to a variety of substituted p-phenyl
17、enediamine (PPD) antidegradants used inthe rubber industry. The three general classes of PPD are dialkyl, alkyl-aryl and diaryl, which are used to impartozone resistance to rubber. The test methods of greatest significance in assessing the purity of production PPDs,and hence their suitability for us
18、e in rubber, are specified in this International Standard.2 Normative referencesThe following normative documents contain provisions which, through reference in this text, constitute provisions ofthis International Standard. For dated references, subsequent amendments to, or revisions of, any of the
19、sepublications do not apply. However, parties to agreements based on this International Standard are encouraged toinvestigate the possibility of applying the most recent editions of the normative documents indicated below. Forundated references, the latest edition of the normative document referred
20、to applies. Members of ISO and IECmaintain registers of currently valid International Standards.ISO 1042:1998, Laboratory glassware One-mark volumetric flasks.ISO 1772:1975, Laboratory crucibles in porcelain and silica.ISO 6472:1994, Rubber compounding ingredients Abbreviations.ISO/TR 9272:1986, Rub
21、ber and rubber products Determination of precision for test method standards.ISO 15528:1G29, Paints, varnishes and raw materials for paints and varnishes Sampling.3 Terms and definitionsFor the purposes of this International Standard, the following terms and definitions apply:3.1area normalizationme
22、thod of calculating the percent composition by measuring the area of each component peak observed in achromatogram and dividing the area of the peak by the total peak area for all the components observed1) To be published. (Revision of ISO 842:1984 and ISO 1512:1991)Copyright International Organizat
23、ion for Standardization Provided by IHS under license with ISONot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO 11236:2000(E)2 ISO 2000 All rights reserved3.2lot sampleproduction sample representative of a standard production unit3.3test portionactual material us
24、ed in the analysisNOTE The test portion must, of course, be representative of the lot sample.4 AbbreviationsThe following abbreviations, taken from ISO 6472, are used in the text:77PD N,N-bis(1,4-dimethylpentyl)-p-phenylenediamineDTPD N,N-ditolyl-p-phenylenediamineIPPD N-isopropyl-N-phenyl-p-phenyle
25、nediaminePPD p-phenylenediamine6PPD N-(1,3-dimethylbutyl)-N-phenyl-p-phenylenediamine5 Use and classificationPPDs represent the primary additive used in tyres and other mechanical rubber goods to impart ozone protectionand to improve resistance to fatigue cracking. PPDs are also used as antioxidants
26、 in a number of applications.Although all PPDs exhibit similar performance characteristics, particular types are frequently preferred for certainend-use conditions, for example the type and degree of flexing experienced by the rubber article.PPDs are classified into the following types:Type I: N,N-d
27、ialkyl PPDs (see Figure 1)R and R are secondary alkyl groups, usually C6or larger. These materials are generally liquids at ambientconditions and consist for the most part (G3e 90 %) of a single chemical component.Type II: N-alkyl-N-aryl PPDs (see Figure 2)R is a secondary alkyl group and R is an ar
28、yl substituent (usually phenyl). These materials generally consist of asingle component or a mixture containing two or more major components (mainly isomers).Type III: N,N-diaryl PPDs (see Figure 3)R and R can be the same aryl group or different (usually phenyl or p-tolyl) and can be single componen
29、ts ormixtures of three or more isomers. This type of PPD is generally solid at ambient conditions.Figure 1 Type I: N,N-dialkyl p-phenylenediaminesCopyright International Organization for Standardization Provided by IHS under license with ISONot for ResaleNo reproduction or networking permitted witho
30、ut license from IHS-,-,-ISO 11236:2000(E) ISO 2000 All rights reserved 3Figure 2 Type II: N-alkyl-N-aryl p-phenylenediaminesFigure 3 Type III: N,N-diaryl p-phenylenediamines6 Sampling and repeat determinationsCarry out sampling in accordance with ISO 15528. To ensure homogeneity, blend at least 250
31、g of the lot samplethoroughly prior to removing any test portions.If the difference between the results of duplicate determinations exceeds the repeatability given for the methodconcerned, repeat the test. If no repeatability figure is given for a particular method, report the results of bothdetermi
32、nations.7 Determination of purity by gas chromatography (GC)7.1 GeneralThis method is designed to assess the relative purity of production PPDs by determining the purity of type I, II andIII PPDs using temperature-programmed gas chromatography with either a packed column (procedure A) or acapillary
33、column (procedure B). Quantification is achieved by area normalization using a peak integrator orchromatography data system.Since the results are based on area normalization, the method assumes that all components are eluted from thecolumn and each component has the same detector response. Although
34、this is not strictly true, the errorsintroduced are relatively small and much the same for all samples. Thus they can be ignored, since the intent of themethod is to establish relative purity.Although trace amounts of “low boilers“ are present in production samples, they are disguised by the solvent
35、 peakwhen using packed columns (procedure A).7.2 InterferenceUtilizing the chromatographic conditions prescribed, there are no significant co-eluting peaks. However,degradation of column performance could result in interference problems. Thus, when using the packed column it isessential that the tot
36、al system be capable of 5000 theoretical plates. Evaluation of system efficiency is described inthe note to 7.3.2.7.3 Apparatus7.3.1 Gas chromatograph.Procedure A: Any high-quality temperature-programmed gas chromatograph equipped with a thermal-conductivitydetector and a peak integrator or chromato
37、graphy data system is sufficient for this analysis.Copyright International Organization for Standardization Provided by IHS under license with ISONot for ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO 11236:2000(E)4 ISO 2000 All rights reservedAlthough a thermal-condu
38、ctivity detector is recommended, a flame-ionization detector (FID) can be used ifappropriate adjustment is made for flow rate and sample size. This will probably involve using a smaller-diametercolumn, in which case the adjustment in flow rate and injection volume shall be proportional to the cross-
39、sectionalarea of the column.Procedure B: Any high-quality temperature-programmed gas chromatograph with a flame-ionization detector andequipped for capillary columns is suitable. When utilizing standard capillary columns (0,25 mm), a split injectionsystem is required. However, a “cold on-column“ inj
40、ector is preferred for the wide-bore (0,53 mm) capillaries. TheFID shall have sufficient sensitivity to give a minimum peak-height response of 30 G6dV for 0,1 mass % of 6PPDwhen operated at the stated conditions. Background noise at these conditions shall not exceed 3 G6dV.7.3.2 Gas-chromatographic
41、columns.Procedure A: Use a 1,8 m Gb4 6,4 mm outside diameter Gb4 4 mm inside diameter glass column packed with 10 %methyl silicone fluid (100 %) on a 0,15/0,08 mm (80/100 mesh) acid-washed and silanized diatomite support.Condition the column with a helium flow of approximately 20 cm3/min by programm
42、ing from ambient temperature to350 C at the rate of 2 C/min to 3 C/min and holding at 350 C overnight with the detector disconnected.NOTE When using a packed column, a minimum of 5 000 theoretical plates, as measured from the analyte peak, under thechromatographic conditions stated in Table 1, is re
43、quired for analysis. The number of theoretical plates (TP) is determined bythe following equation:TP = 5,5 X(R)/Y(0,5)2whereX(R) is the retention time measured from the injection point to the apex of the 6PPD peak (adjust the attenuation to keeppeak on scale) in mm;Y(0,5) is the 6PPD peak width at h
44、alf height, in mm.Procedure B: Use a 30 m Gb4 0,25 mm fused-silica capillary internally coated to a film thickness of 0,25 G6dm (bonded)with methyl silicone (column 1), or a 15 m Gb4 0,53 mm fused-silica (megabore) capillary coated with a 3,0 G6dmbonded film of 5 % phenyl silicone, HP-5 or equivalen
45、t (column 2).7.3.3 Integrator/data system, capable of determining the relative amount of each component by integration ofthe detector output as a function of time. When using capillary columns (procedure B), the equipment shall becapable of integrating at a sufficiently fast rate so that narrow peak
46、s (1 s peak width) are accurately measured.7.3.4 Volumetric flask, capacity 10 cm3, meeting the requirements of ISO 1042.7.3.5 Mortar and pestle.7.3.6 Precision balance, accurate to Gb11 mg or better.7.3.7 Syringe, of suitable size (see relevant procedure).7.4 Calibration and standardizationChromato
47、grams from typical PPD antidegradants run on the packed columns in accordance with the prescribedprocedure are given in Figures 4 and 5.NOTE When using the conditions described for procedure A (packed column), the detector response for injections of500 G6dgto5000G6dg of 6PPD was found to be somewhat
48、 non-linear. However, over the more limited range 750 G6dgto2500G6dg,the response was nearly linear. It is important that the samples be prepared so that 1250 G6dg to 1500 G6dg injections are made.Copyright International Organization for Standardization Provided by IHS under license with ISONot for
49、ResaleNo reproduction or networking permitted without license from IHS-,-,-ISO 11236:2000(E) ISO 2000 All rights reserved 57.5 Procedure7.5.1 Sample preparationTo ensure homogeneity, grind lot samples of 6PPD with a mortar and pestle prior to weighing out the test portion.In the case of liquid 6PPD where partial crystallization may have occurred resu
