1、Designation: D7823 18Standard Test Method forDetermination of Low Level Phthalates in Poly (VinylChloride) Plastics by Thermal DesorptionGasChromatography/Mass Spectrometry1This standard is issued under the fixed designation D7823; the number immediately following the designation indicates the year
2、oforiginal adoption or, in the case 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. Scope*1.1 This test method provides a procedure to identify andqua
3、ntify phthalates by thermal desorption (TD) gas chroma-tography (GC) mass spectrometry (MS). Six phthalates areused to demonstrate the use of the procedure: BBP, DBP,DEHP, DNOP, DINP and DIDP.1.2 Within the context of this method, “low level” is definedas 1000 ppm.1.3 The values in SI units are to b
4、e regarded as standard.1.4 This test method includes references, notes and foot-notes that provide explanatory material. These notes andfootnotes (excluding those in the tables and figures) shall notbe considered as requirements of this method.1.5 This standard does not purport to address all of the
5、safety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.NOTE 1The method can be extended to include other ortho
6、-phthalatesin a number of polymeric substrates.NOTE 2There is no known ISO equivalent to this standard.1.6 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of Internati
7、onal Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D883 Terminology Relating to PlasticsD1600 Terminology forAbbreviated Terms Relating to Plas-ticsD3465 Test Method for Purity of Mo
8、nomeric Plasticizers byGas ChromatographyD7083 Practice for Determination of Monomeric Plasticiz-ers in Poly (Vinyl Chloride) (PVC) by Gas Chromatogra-phyE177 Practice for Use of the Terms Precision and Bias inASTM Test MethodsE355 Practice for Gas Chromatography Terms and Relation-shipsE594 Practic
9、e for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid ChromatographyE691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test MethodIEEE/ASTM SI10 Practice for Use of the InternationalSystem of Units (SI), the Modernized Metric System2.2 ASTM Adju
10、ncts:Adjunct to D7823 Vinyl Plasticizer LibraryTotal IonChromatograms and Mass Spectra33. Terminology3.1 DefinitionsFor definition of plastic terms used in thistest method, see Terminologies D883 and D1600.3.2 For units, symbols, and abbreviations used in this testmethod refer to Practices E594, E35
11、5,orSI10.3.3 Compounds and Instrumentation:3.3.1 (DOA) Hexanedioic acid, 1,6bis(2ethylhexyl) esterCAS #1032313.3.2 (DINCH) 1,2Cyclohexanedicarboxylic acid, dinonylester, branched and linear CAS #4749195903.3.3 (DBP) 1,2Benzenedicarboxylic acid, 1,2dinbutylester CAS #847423.3.4 (BBP) Benzyl butyl pht
12、halate CAS #856873.3.5 (DEHP) Bis(2ethyhexyl) phthalate CAS #1178173.3.6 (DNOP) Di(noctyl) phthalate CAS #1178401This test method is under the jurisdiction of ASTM Committee D20 on Plasticsand is the direct responsibility of Subcommittee D20.70 on Analytical Methods.Current edition approved Nov. 1,
13、2018. Published November 2018. Originallyapproved in 2013. Last previous edition approved in 2016 as D7823 16. DOI:10.1520/D7823-18.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume inform
14、ation, refer to the standards Document Summary page onthe ASTM website.3Available from ASTM International Headquarters. Order Adjunct No.ADJD7823S-EA. Original adjunct produced in 2016.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Driv
15、e, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations iss
16、ued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.13.3.7 (DINP) 1,2Benzenedicarboxylic acid,diC810branched alkyl esters, C9rich (Jayflex) CAS#685154803.3.8 (DINP) 1,2Benzenedicarboxylic acid, 1,2diisononyl(Palatinol) CAS #285531203.3.9 (DIDP) 1,2Benzenedicarboxylic acid
17、,diC911branched alkyl esters, C10rich (Jayflex) CAS#685154913.3.10 (DIDP) 1,2Benzenedicarboxylic acid, 1,2diisodecylCAS #267614003.3.11 TD Thermal Desorption3.3.12 GC Gas Chromatography3.3.13 GC/MS Gas Chromatography/Mass Spectrometry3.3.14 PVC Poly (vinyl chloride)3.3.15 THF GC grade or higher “Tet
18、rahydrofuran”3.3.16 DCM GC grade or higher “Methylene Chloride”3.3.17 EGAMS Evolved Gas Analysismass spectrometry3.3.18 FTIR Fourier Transform Infrared Spectroscopy3.3.19 TIC Total ion chromatogram3.3.20 DQO Data quality objectives4. Summary of Test Method4.1 200 mg of the PVC sample are dissolved i
19、n 10 mL ofTHF. 10 L of the THF solution are analyzed using TD-GC/MS. Phthalates are identified by their retention times and theirmass spectra. Quantification is based on the area of a desig-nated quant ion (SIM or full scan)see Table 1. Standardaddition is the calibration method.NOTE 3Standard addit
20、ion calibration will negate matrix interference.It also takes into account the overall performance of the instrumentationat the time the samples are analyzed.5. Significance and Use5.1 Identification and Quantitation of PhthalatesDBP,BBP, DEHP, DNOP, DINP, and DIDP are representative of thephthalate
21、s either banned or being monitored by a variety ofregulations. Regulations include: EUDirective 2005/84/EC,USConsumer Product Safety Improvement Act of 2008 section 108, JapanHealth, Labor and Welfare Ministryguideline No. 336 (2010) and IEC 62321-8:2017. These testmethods provide a procedure to ide
22、ntify and quantify phtha-lates in PVC.5.2 Other techniques successfully used to separate andidentify phthalates in PVC include GC/MS, HPLC/UV, HPLC/MS, FTIR, and GC/FID (flame ionization detector).6. Interferences6.1 Retention times for GC are dependent on several vari-ables and it is possible to ha
23、ve two or more components withidentical retention times. The analyst shall take the necessarysteps to make certain that adequate separation of the plasticizercomponents is achieved or the ions used to monitor for a targetphthalate are free of interference. This includes but is notlimited to changing
24、 the selectivity of the chromatographiccolumn and the thermal profile of the column during analysis.Calibration by standard addition helps to minimize interfer-ences.6.2 When using a TDGC/MS method, care must be taken toensure that the sample cups are clean. Recent experimentationindicates that equi
25、valent results are obtained using sample cupsmade of clean “untreated” stainless steel, glass or deactivatedstainless steel. The cleanliness of the cup surface is moreimportant than the chemistry of the cup material itself.Any andall solvents and chemware used to prepare standards andsample solution
26、s must be free of phthalate contamination.Avoid using plastic labware.6.3 The presence or absence of each phthalate is based uponthree criteria: (1) the relative retention time of the peak (2) thepresence or absence of the quant ion and the two confirmingions and (3) the ratio of the quant and the c
27、onfirming ion onemust satisfy the established guideline (see Table 1).6.4 Calculating the phthalate concentrations using the areasof compound specific ions and standard addition significantlyreduces interference from nontarget compounds.7. Apparatus7.1 Gas chromatograph/mass spectrometer capable of
28、oper-ating in the 75 to 350C range.NOTE 4Optional but recommended: Ventfree GC/MS Adapter. Thisfacilitates the rapid conversion between detailed analysis and evolved gasanalysis.7.2 Thermal desorption unit capable of heating the samplefrom 100 to 350C at 20C/min.7.3 Inert, reusable or disposable sam
29、ple containers or cups.7.4 GC capillary column: 5 % diphenyl95 % poly (dimeth-ylsiloxane) stainless steel, 30 m by 0.25 mm ID with a 0.25 mfilm thickness, or equivalent.7.5 Integrator or data handling system, capable of measur-ing peak areas and retention times to four significant figures.7.6 Analyt
30、ical balance, capable of weighing to 60.000001 g(1 g). If using a balance capable of weighing to 60.00001 g(10 g), weight used in the sample and standard preparationmust be scaled accordingly in order to ensure that the data areaccurate to three significant figures.7.7 Pressure regulators, for all r
31、equired gas cylinders.7.8 Flow meter, or other means of measuring gas flow rates60.1 mL/min.8. Reagents and Materials8.1 Helium carrier gas, chromatographic grade.TABLE 1 Ions and Ion Ratios Used to Identify Each PhthalateDBP BBP DEHP DNOP DINP DIDPQuant ion 223 206 279 279 293 307Confirmion 1149 14
32、9 149 149 149 149Area ratio(10%)(Quant/Confirm1)0.04 0.23 0.08 0.06 0.20 0.12Confirmion 2167 167 167 167 167 167D7823 1828.2 Methylene chloride (DCM) or nhexane for preparingthe phthalate standard solution (Solution #1, 10.2), spectralquality or chromatographic grade.8.3 Tetrahydrofuran (THF), or a
33、solvent suitable for prepar-ing the PVC sample (Solution #2, 10.3), spectral quality orchromatographic grade.8.4 Standards of the appropriate phthalates for use whenconstructing an external calibration curve or when preparingSolution #3 (10.4) that is used for the standard additionprocedure. Use tec
34、hnical grade DINP and DIDP when prepar-ing the calibration standard.NOTE 5DINP and DIDP, when used in various PVC formulations aretechnical mixtures. Here is specific information on DINP and DIDP. Formore information, please refer to Appendix X3.Jayflex DIDP: 1,2 Benzenedicarboxylic acid, di C9 11 b
35、ranchedalkyl esters, C10 rich: CAS# 68515 49 1.Jayflex DINP: 1,2 Benzenedicarboxylic acid, di C8 10 branchedalkyl esters, C9 rich: CAS# 68515 48 0.9. Safety and Precautions9.1 Use THF and methylene chloride in a wellventilatedspace.10. Preparation of the Analytical Samples (based uponusinga1gbalance
36、) Weights must be scaled up ifusing a 10-g balance.10.1 Three solutions must be prepared: (1) a stock solutionof the target phthalate standards, (2) a solution of the sampleand (3) the sample solution spiked with the standard stocksolution.10.2 Solution #1Prepare a stock standard solution of thephth
37、alates by dissolving 0.30 mg of each phthalate in 10 mL ofmethylene chloride (0.30 mg/10 mL). Nhexane has also beenused with success. See Fig. 1 for a typical chromatogram.10.3 Solution #2Dissolve 200 mg of the sample in 10 mLTHF (200 mg/10 mL). Shake (or sonicate) the solution for fiveFIG. 1 Soluti
38、on #1Phthalates Standard Mixture in DCM (see 10.2)D7823 183minutessee Note 6. The solution is likely to range from clearto slightly cloudy. Place 10 L of the sample solution in a cleansample cup. Evaporate the solvent; the sample is ready toanalyze. See Figs. 2 and 3 for example chromatograms.NOTE 6
39、A critical step in the accurate determination of phthalates issample homogeneity. This is discussed in more detail in Appendix X2.NOTE 7It is possible that the solution will contain inorganic material.Studies have shown that the presence of insoluble inorganic material willnot affect either the accu
40、racy or precision of the phthalate determination.10.4 Solution #3Place 10 L of the sample solution (#2)into a clean sample cup. Add 10 L of the phthalate standardsolution (#1). Evaporate the solvent.NOTE 8To expedite the evaporation process, pass a steady stream ofa high purity inert gas using clean
41、, (plasticizer- and additive-free) tubingover the sample cup.FIG. 2 Solution #2Chromatograms (TIC) of PVC with Three Different Plasticizers, TD-GC/MS Analysis (see 10.3 and 11.3)D7823 18411. Procedure11.1 Establish that the analytical system contains concen-trations of phthalate contamination that a
42、re lower than thebackground contamination acceptable to the project specificData Quality Objectives by analyzing 10 L of THF.11.2 Establish the relative retention time and mass spectrumof each phthalate using Solution #110.2: The followingconditions were used to obtain the example chromatogramsshown
43、 in Figs. 1-4:FIG. 3 Solution #2Reproducibility of PVC-DINCH (n=6) (see 10.3 and 11.3)D7823 185Thermal Desorption (TD)GC/MS ParametersTD temperature: 100 20C/min 320C (5 min hold)Py interface: 320C (Auto mode),GC injector : 300CGC oven: 80 (1 min hold) to 200C (at 50C/min).Injection at 80C avoids th
44、ermalshock, which improves analyticalprecision. The initial ramp rate is notcritical and will be a function of theperformance of the GC oven.200C to 320C (15C/min), 2 minhold 320CSolvent delay: 6 minColumn: UA5 (5 % Diphenyl95 % dimethylpolysiloxane) 30 m by 0.25 mm i.d,0.25 m film) or equivalentCol
45、umn He flow: 1.2 mL/min, Split ratio: 1/20Mass range: 29600 m/z,Scan speed: 2.57 scans/sec,Threshold: 50MSD Transfer Line Temp.: 300CIon Source (EI) temp.: 230CFIG. 4 Solution #3Standard Addition (see 11.7)D7823 18611.2.1 Confirm the TD zone using Evolved Gas Analysis(EGA)MS. The total ion chromatog
46、ram of the sample (Solu-tion #2, 10.3) needs to be similar to that presented in AppendixX1. The thermal zone normally will not vary from sample-to-sample; thus, EGA need not be performed on every sample inthe batch. A check sample when the polymer substrate changesshould be performed in order to ver
47、ify the limits of the thermalzone.11.3 Analyze the sample (Solution #2, 10.3) using theconditions outlined in 11.2. Typical chromatograms are shownin Figs. 2 and 3. The precision of the TD method is shown inFig. 3.11.4 Peak identifications are based on relative retentiondata, full scan extracted ion
48、 chromatograms of both the quantand confirming ions and the ion area ratios as indicated inTable 1. Phthalate quantitation is based upon the peak areas ofthe quant ions listed in Table 1. The assumption being made isthat the sole source of the quant ion at a predeterminedretention time is the phthal
49、ate. Use the peak area of the quantion can be used to accurately determine the amount of thephthalate.11.5 If using selected ion monitoring (SIM), peak identifi-cation is based solely on the presence or absence of the quantion and the two confirming ions at predetermined retentiontimes. Quantitation is based on the area of the quant ion.11.6 When DINP and DIDP are both present in a sample orstandard, use m/z 127 as a qualifying ion for DINPand m/z
