ASTM D5297-1995(2009) Standard Test Methods for Rubber Chemical Accelerator-Purity by High Performance Liquid Chromatography《用高性能液相色谱法对亚磺酰胺加速剂纯度的标准试验方法》.pdf

1、Designation: D 5297 95 (Reapproved 2009)Standard Test Methods forRubber Chemical AcceleratorPurity by High PerformanceLiquid Chromatography1This standard is issued under the fixed designation D 5297; the number immediately following the designation indicates the year oforiginal adoption or, in the c

2、ase of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover the determination of the purityof present commercially available

3、 rubber chemical acceleratorsin the range from 80 to 100 % by high performance liquidchromatography (HPLC) using ultraviolet detection and exter-nal standard calculations.1.2 Expertise in HPLC is necessary to the successful appli-cation of these test methods.1.3 The values stated in SI units are to

4、be regarded asstandard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and

5、determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 3853 Terminology Relating to Rubber and RubberLaticesAbbreviations for Chemicals Used in Com-poundingD 4483 Practice for Evaluating Precision for Test MethodStandards in the Rubber and Ca

6、rbon Black ManufacturingIndustriesD 4571 Test Methods for Rubber CompoundingMaterialsDetermination of Volatile MaterialD 4936 Test Method for Mercaptobenzothiazole Sulfena-mide Assay by Reduction/Titration2.2 ISO Standard:3ISO 6472 Rubber Compounding IngredientsAbbreviations3. Terminology3.1 Definit

7、ions:3.1.1 external standard calculationa method of calculat-ing the percent composition by measuring the area of theanalyte peak, multiplying by a response factor, and dividing bythe sample concentration. All components are assumed to beresolved from the component of interest.3.1.2 lot samplea prod

8、uction sample representative of astandard production unit, normally referred to as the sample.3.1.3 specimenalso known as the test portion, it is theactual material used in the analysis. It must be representative ofthe lot sample.3.2 Abbreviations: The following abbreviations are in ac-cordance with

9、 Terminology D 3853 and ISO 6472:3.2.1 MBTSBenzothiazyl disulfide.3.2.2 MBS2-(morpholinothio)benzothiazole.3.2.3 CBSN-cyclohexyl-2-benzothiazolesulfenamide.3.2.4 TBBSN-t-butyl-2-benzothiazolesulfenamide.3.2.5 DIBSN,N8- diisopropyl-2-benzothiazolesulfena-mide.3.2.6 DCBSN,N8 - dicyclohexyl-2-benzothia

10、zolesulfe-namide.3.2.7 DPGdiphenylguanidine.3.2.8 DOTGdi-o-tolylguanidine.4. Summary of Test Methods4.1 A specimen is dissolved in the appropriate solvent and afixed loop volume is analyzed by isocratic HPLC using athermostated C18 reversed phase column for materials 3.2.1-3.2.6 and a silica normal

11、phase column for materials 3.2.7 and3.2.8, and an ultraviolet (UV) detector. Peak areas are deter-mined using a chromatographic integrator or laboratory datasystem with the amount of analyte being determined byexternal calibration.5. Significance and Use5.1 These test methods are designed to determi

12、ne the purityof rubber chemical accelerators.1These test methods are under the jurisdiction of ASTM Committee D11 onRubber and are the direct responsibility of Subcommittee D11.11 on ChemicalAnalysis.Current edition approved July 1, 2009. Published September 2009. Originallyapproved in 1992. Last pr

13、evious edition approved in 2004 as D 5297 95 (2004).2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Availabl

14、e from American National Standards Institute (ANSI), 25 W. 43rd St.,4th Floor, New York, NY 10036.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5.2 Since the results of these test methods are based on anintegrated peak area, it is

15、assumed that all analytes of interestare resolved from interfering peaks.6. Interferences6.1 Components co-eluting with the analyte of interest willcause erroneous results; thus it is required that the system becapable of providing a minimum of 10 000 theoretical plates.7. Apparatus7.1 Liquid Chroma

16、tograph, consisting of the following:7.1.1 Precision chromatographic pump,7.1.2 Variable wavelength UV detector,7.1.3 A method for thermostating the column at 35 6 1C,for example, a column oven or water jacket, and7.1.4 A fixed loop injector with a nominal volume of 10mm3(L) or less.7.2 HPLC Column:

17、7.2.1 A C18 (ODS) reversed phase column packed withspherical, totally porous monomolecular 5-m particles ca-pable of providing 40 000 theoretical plates per metre. (Aminimum of 10 000 plates is required for this analysis.) Thiscolumn should be reserved for this analysis.7.2.2 For materials 3.2.7 and

18、 3.2.8, use a silica normal phasecolumn packed with spherical, totally porous 5-m particlescapable of providing 40 000 theoretical plates per metre. (Aminimum of 10 000 plates is required for this analysis.) Thiscolumn should be reserved for this analysis.7.3 Integrator/Data System, capable of deter

19、mining abso-lute amounts of analyte of interest by means of integration ofdetector output versus time.7.4 Analytical Balance, capable of measuring within 60.01mg.8. Reagents and Materials8.1 Acetic Acid, glacial.8.2 Acetonitrile, HPLC grade.8.3 Chloroform, AR grade.8.4 Ethanol, HPLC grade.8.5 Ethano

20、lamine.8.6 n-Hexane, HPLC grade.8.7 Methanol, HPLC grade.8.8 Water, HPLC grade.9. Calibration and Standardization9.1 Aprimary standard of known purity is used to determinethe response factor for each analyte.TEST METHOD ASULFENAMIDEACCELERATORPURITY10. Procedure10.1 Chromatographic Conditions:10.1.1

21、 Determine the mobile phase composition and theflow rate by adjusting the chromatographic parameters for theparticular column chosen. The mobile phase consists of theappropriate mixture of HPLC grade acetonitrile and HPLCgrade or equivalent water, both containing 0.001 M glacialacetic acid or less d

22、epending on the particular column chosen.(HPLC grade methanol may be added to the acetonitrile/watereluent to achieve the necessary separation for DIBS andMBTS.)10.1.2 For the analysis of the sulfenamides, adjust the flowrate and mobile phase composition to provide a capacity factor,k8, in the range

23、 from 4 to 6 for the analyte of interest, and aminimum resolution, Rs, of 2 between the MBTS impurity andthe analyte of interest.NOTE 1Different liquid chromatography columns may exhibit differ-ent elution characteristics. Suggested chromatographic starting parametersfor analysis are as follows:Perc

24、entH2OAPercentAcetonitrileAPercentMethanolAFlow rate(cm3/min)DCBS 5 95 0 2.5CBS 20 80 0 2.0TBBS 30 70 0 1.7MBS 45 55 0 1.4DIBS 15 0 85 1.0AContaining 0.001 M glacial acetic acid.10.1.3 The capacity factor, k8, is defined as the retentiontime of the analyte, tA, minus the retention time of anunretain

25、ed solute (solvent peak), to, divided by to:k8 5 tA2 to!/to(1)10.1.4 The resolution, Rs, is a function of the capacityfactor, selectivity, and the theoretical plates of the column:Rs5t22 t1!1/2 tw11 tw2!(2)where:t1,t2= retention times of the analyte and MBTS, andtw1,tw2= peak widths at 10 % of the p

26、eak height.10.2 DetectorMonitor the absorbance of all componentsat 275 nm. The detector sensitivity should be set to 1absorbance unit full scale (AUFS).10.3 Integrator/Data SystemThe integrator settingsshould be adjusted to give a full-scale response to 1 absorbanceunit (AU).10.4 Standard Preparatio

27、nWeigh at least 50 mg to thenearest 0.01 mg of the standard in a 50-cm3volumetric flaskand dilute to volume with acetonitrile. Adjust the standardconcentration if necessary by serial dilution with acetonitrile togive a maximum absorbance (peak height) between 0.4 and 0.8AU (the linear range of the c

28、hromatographic system). Thestandard must be analyzed within4hofbeing diluted.NOTE 2Preparation of StandardsThe analytical standards are pre-pared by multiple recrystallizations of the sulfenamides. Dissolve 100 g ofthe sulfenamide in 200 cm3of analytical reagent (AR) grade toluene withslight warming

29、. Add2gofactivated carbon and stir for 30 min. Filter thehot solution by gravity and cool in an ice/acetone bath. Filter the crystalswith suction. Repeat this crystallization. Dissolve the analyte crystals fromthe second toluene crystallization in hot methanol, cool in an ice/acetonebath, and filter

30、 with suction. Repeat the alcohol recrystallization and dryat low pressure at 50C overnight. The procedure can be repeated until thedesired purity is obtained. The purity of the standard is estimated bygradient HPLC analysis of the impurities and differential thermal analysis(DTA). The purity of the

31、 standard should be reestimated by HPLC of theimpurities every 90 days. The standard should be stored at 5C or lower.Volatile matter and free amine content can be measured using TestMethods D 4571 and Test Method D 4936, respectively.10.5 Test PreparationTo ensure specimen homogeneity, 5g of the lot

32、 sample should be ground with a mortar and pestle.D 5297 95 (2009)210.6 Analysis:10.6.1 Weigh at least 50 mg to the nearest 0.01 mg of thespecimen into a 50-cm3volumetric flask. Dissolve in acetoni-trile (a sonic bath is recommended) and dilute to volume withacetonitrile. Adjust the concentration, i

33、f necessary, by serialdilution with acetonitrile to give a maximum absorbance within10 % of the standard absorbance. Filter through a chemicallyresistant filter with a nominal pore size less than or equal to 0.5m. Analyze within4hofdilution. Chromatograph thestandard and measure the area.TEST METHOD

34、 BBENZOTHIAZOLEACCELERATORPURITY11. Procedure11.1 Chromatographic Conditions:11.1.1 Determine the mobile phase composition and theflow rate by adjusting the chromatographic parameters for theparticular column chosen. The mobile phase consists of theappropriate mixture of HPLC grade acetonitrile and

35、HPLCgrade or equivalent water, both containing 0.001 M glacialacetic acid or less depending on the particular column chosen.11.1.2 For the analysis of the benzothiazoles, adjust the flowrate and mobile phase composition to provide a capacity factor,k8, in the range from 4 to 6 for the analyte of int

36、erest, and aminimum resolution, Rs, of 2 between the MBTS impurity andthe analyte of interest.NOTE 3Different liquid chromatography columns may exhibit differ-ent elution characteristics. Suggested chromatographic starting parametersfor analysis are as follows:PercentH2OAPercentAcetonitrileAPercentM

37、ethanolAFlow rate(cm3/min)MBT 65 35 0 2.0MBTS 20 80 0 2.0AContaining 0.001 M glacial acetic acid.11.1.3 The capacity factor, k8, is defined as the retentiontime of the analyte, tA, minus the retention time of anunretained solute (solvent peak), to, divided by to:k8 5 tA2 to! / to(3)11.1.4 The resolu

38、tion, Rs, is a function of the capacityfactor, selectivity, and the theoretical plates of the column:Rs5t22 t1!1/2 tw11 tw2!(4)where:t1,t2= retention times of the analyte and MBTS, andtw1,tw2= peak widths at 10 % of the peak height.11.2 DetectorMonitor the absorbance of all componentsat 275 nm. The

39、detector sensitivity should be set to 1absorbance unit full scale (AUFS).11.3 Integrator/Data SystemThe integrator settingsshould be adjusted to give a full-scale response to 1 absorbanceunit (AU).11.4 Standard PreparationWeigh at least 50 mg to thenearest 0.01 mg of the standard in a 50-cm3volumetr

40、ic flaskand dilute to volume with acetonitrile for MBT and chloroformfor MBTS. Adjust the standard concentration if necessary byserial dilution with acetonitrile to give a maximum absorbance(peak height) between 0.4 and 0.8 AU (the linear range of thechromatographic system). The standard must be ana

41、lyzedwithin4hofbeing diluted.NOTE 4Preparation of StandardsThe analytical standards may beprepared by multiple recrystallizations of the benzothiazoles. The purity ofthe standard is estimated by gradient HPLC analysis of the impurities anddifferential thermal analysis (DTA). The purity of the standa

42、rd should bereestimated by HPLC of the impurities every 90 days. The standard shouldbe stored at 5C or lower.11.5 Test PreparationTo ensure specimen homogeneity, 5g of the lot sample should be ground with a mortar and pestle.11.6 Analysis:11.6.1 Weigh at least 50 mg to the nearest 0.01 mg of thespec

43、imen into a 50-cm3volumetric flask. Dissolve MBT inacetonitrile and MBTS in chloroform (a sonic bath is recom-mended) and dilute to volume with acetonitrile for MBT andchloroform for MBTS. Adjust the concentration, if necessary,by serial dilution with acetonitrile to give a maximum absor-bance withi

44、n 10 % of the standard absorbance. Filter with achemically resistant filter with a nominal pore size less than orequal to 0.5 m. Analyze within4hofbeing diluted.Chromatograph the standard and measure the area.TEST METHOD CGUANIDINE ACCELERATORPURITY12. Procedure12.1 Chromatographic Conditions:12.1.1

45、 Determine the mobile phase composition and theflow rate by adjusting the chromatographic parameters for theparticular column chosen. The mobile phase consists of theappropriate mixture of HPLC grade n-hexane, ethanol, andmethanol containing 0.01 M ethanolamine or less depending onthe particular col

46、umn chosen.12.1.2 For the analysis of the guanidines, adjust the flowrate and mobile phase composition to provide a capacity factor,k8, in the range from 6 to 8 for the analyte of interest.NOTE 5Different liquid chromatography columns may exhibit differ-ent elution characteristics. Suggested chromat

47、ographic starting parametersfor analysis are as follows:Percentm-HexanePercentEthanolAPercentMethanolAFlow rate(cm3/min)DPG 91 4 5 2.0DOTC 91 4 5 2.0AContaining 0.01 M ethanolamine.12.1.3 The capacity factor, k8, is defined as the retentiontime of the analyte, tA, minus the retention time of anunret

48、ained solute (solvent peak), to, divided by to:k8 5 tA2 to! / to(5)12.2 DetectorMonitor the absorbance of all componentsat 240 nm. The detector sensitivity should be set to 1absorbance unit full scale (AUFS).12.3 Integrator/Data SystemThe integrator settingsshould be adjusted to give a full-scale re

49、sponse to 1 absorbanceunit (AU).12.4 Standard PreparationWeigh at least 50 mg to thenearest 0.01 mg of the standard in a 50-cm3volumetric flaskand dilute to volume with 45/55 (v/v) ethanol/methanol.Adjustthe standard concentration if necessary by serial dilution withD 5297 95 (2009)3m-hexane to give a maximum absorbance (peak height) be-tween 0.4 and 0.8 AU (the linear range of the chromatographicsystem). The standard must be analyzed within4hofbeingdiluted.NOTE 6Preparation of StandardsThe analytical standards are pre-pared