1、Designation: D8154 17Standard Test Methods for1H-NMR Determination of Ketone-Ethylene-Ester andPolyvinyl Chloride Contents in KEE-PVC Roofing Fabrics1This standard is issued under the fixed designation D8154; the number immediately following the designation indicates the year oforiginal adoption or,
2、 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. Scope1.1 This test method pertains to the determination of therelative contents of Ketone
3、-Ethylene-Ester (KEE) and Polyvi-nyl Chloride (PVC) after their extraction from reinforcedroofing membranes, or fabrics. Based on Proton NuclearMagnetic Resonance Spectroscopy (1H-NMR), the methodallows for the quantification of PVC with respect to an internalstandard. The KEE content is then obtain
4、ed by difference. Thetest method is not applicable to membranes or blends thatcontain high molecular weight polymers other than PVC andKEE.1.2 UnitsThe values stated in SI units are to be regardedas standard. No other units of measurement are included in thisstandard.1.3 This standard does not purpo
5、rt 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, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.1.4 This international standard
6、 was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Refer
7、enced Documents2.1 ASTM Standards:2D1079 Terminology Relating to Roofing and WaterproofingD6754/D6754M Specification for Ketone Ethylene EsterBased Sheet Roofing3. Terminology3.1 DefinitionsTerminology D1079 and SpecificationD6754/D6754M shall apply to this test method.4. Summary of Test Method4.1 T
8、est MethodsThere are two related test methods toquantify PVC and KEE in roofing fabrics. In both methods thepolymer blend is extracted from the fabric and purified by aseries of dissolution, centrifugation, and precipitation. Afterdrying, the blend is dissolved in deuterated tetrahydrofuranalong wit
9、h a1H-NMR internal standard. In Method A, PVCcontent is quantified by comparing its1H-NMR signal with thatof the internal standard, and KEE is obtained by difference.Method B adds to Method A a calibration curve the slope ofwhich providing for a correction factor. This correction factoris applied to
10、 the polymer content obtained by Method A toprovide for greater precision on the PVC and KEE contents.5. Significance and Use5.1 Determination of the percentage of KEE compound insheet roofing is of concern to many specifiers and buildingowners. Method A, the faster method, is best used for qualityc
11、ontrol. Method B may apply better to research anddevelopment, or investigative work.6. Interferences6.1 The NMR analysis of the polymer blend extracted fromthe sheet roofing is sensitive to impurities, includingplasticizer, filler, reinforcement, and trace solvent (other thanthe NMR solvent). The pr
12、ocedure here is meant to purify theblend for proper analysis.7. Equipment and Apparatus7.1 Glassware. Erlenmeyer flask and stopper, 125 mL.Weighing bottle, 25 mL.7.2 Porcelain ware. Bchner funnel, 10 cm in diameter.7.3 Platform shaker. Must accept 125 mL Erlenmeyer, andallow for swirling at 120 to 1
13、50 rpm.7.4 Metal spatula. To stir the suspension during the precipi-tation step.1This test method is under the jurisdiction ofASTM Committee D08 on Roofingand Waterproofing and is the direct responsibility of Subcommittee D08.18 onNonbituminous Organic Roof Coverings.Current edition approved Nov. 1,
14、 2017. Published November 2017. DOI:10.1520/D8154-17.2For 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.Copyrigh
15、t ASTM International, 100 Barr Harbor Drive, 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
16、 Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.17.5 Pasteur pipettes. To transfer solubilized polymer andsolvent from one flask to another.7.6 Centrifuge. Capable of 10 000 RPM.7.7 Centrifuge tubes. 50 mL. Must be resistant t
17、o THF, forexample, Fluorinated Ethylene Propylene.7.8 Watch-glass. To dry polymer in the oven.7.9 Vacuum Oven. Adjustable to 65 6 2C.7.10 Vacuum pump. To provide for 100 kPa of vacuum inthe oven.7.11 Balance. Sensitive to 0.000001 g (1 microgram).7.12 NMR sample tubes. 5 mm in diameter.7.13 NMR Four
18、ier Transform Spectrometer. Equipped witha proton probe. 400 MHz field strength or higher is recom-mended.8. Reagents and Materials8.1 Water. 500 mL, and crushed ice, 1 kg, for an ice bath.8.2 Whatman filter paper No. 2. For the Bckner funnel.8.3 Lint-free paper towel. To blot sample dry of solvent.
19、8.4 Hexane. Technical grade, 60 mL.8.5 Tetrahydrofuran (THF). Technical grade, 150 mL.8.6 Methanol. Technical grade, 450 mL. Maintained near5C in an ice bath.8.7 Deuterated tetrahydrofuran (THF-d8). 99.5 % pure orbetter.8.8 1,2,4,5Tetrachloro-3-nitro-benzene. Certified referencematerial, TCNB, 99.7
20、% pure or better.8.9 Polyvinyl chloride (PVC) powder. For calibration inMethod B. It is ideally obtained from the membrane producer.If this fails, PVC could be obtained from a primary source, thatis, a raw material producer, ascertaining that the product sourceand grade is the same as that used in a
21、ctual sheet roofingproduction. PVC could be obtained for instance from OxyVi-nyls. For best precision in polymer quantification, the rawmaterials for calibration samples should be those used in themembrane fabrication.8.10 Ketone ethylene ester (KEE) pellets. For calibration inMethod B. It is ideall
22、y obtained from the membrane producer.If this fails, KEE could be obtained from a primary source, thatis, DuPontTM(Elvaloy polymer), ascertaining that the prod-uct grade is that used in the sheet roofing fabrication.9. Hazards9.1 Chemical HazardsSeveral solvents are used in thistest method, includin
23、g methanol, THF, hexane, along withTCNB. Check their material safety datasheet to identifyspecific hazards. Follow local regulations for proper disposalof spent chemicals.9.2 CentrifugationCentrifugation of dissolved sheet roof-ing involves high speeds and it must be balanced with counterweights for
24、 safe operation. Refer to the operators manual fordetails. Centrifugation flasks must be resistant to the fluidbeing used and must not swell.9.3 Magnetic FieldsNMR spectroscopy involves strongmagnetic fields. Analysis by NMR requires safety and equip-ment training. Follow local laboratory guidelines
25、.10. Sampling10.1 Samples are obtained from sheet roofing, or frompre-production runs. Cut two pieces of 4 cm2taken 1 m apartalong the length of the same roll. Each piece will be analyzedfor polymer content to provide for duplicate analysis.11. Sample Preparation11.1 Polymer Extraction and Purificat
26、ion Procedure:11.1.1 From each 4 cm2piece of sheet, cut about 0.5 g intosmall pieces, approximately 3 mm 3 mm. Place cut piecesinto a 125 mL Erlenmeyer flask and add 60 mL of hexane.Stopper the flask and place it on a platform shaker to swirl at120 rpm for 24 hours.NOTE 1Hexane is used to clean the
27、sheet and extract low molecularweight plasticizer that would affect the PVC and KEE contents measuredby NMR.11.1.2 Filter off the hexane into a Bchner funnel withcellulose Whatman filter paper No-2. Place the pieces ofsample onto a lint free paper towel and blot them dry.11.1.3 Place sample pieces i
28、nto a 125 mL Erlenmeyer flask,add 45 mLof tetrahydrofuran (THF) and close the flask with itsstopper. Place the flask on a platform shaker and stir its contentat 150 rpm until sample polymer has completely dissolved andthere is no evidence of gel.NOTE 2Dissolution time depends on composition. It may
29、take up to 5hours for the sample to dissolve.11.1.4 Transfer dissolved sample to a 50 mL centrifugationtube. Rinse the Erlenmeyer flask with 5 mL of THF and usethis rinse solvent to completely fill the centrifugation tube. Capthe tube and centrifuge its content for 30 minutes at 10 000rpm. After cen
30、trifugation, carefully transfer the supernatantliquid with a Pasteur pipette to a 125 mL Erlenmeyer flask (fortransport and storage, if necessary), leaving the precipitatedsolid at the bottom of the centrifugation tube.11.1.5 Precipitate the dissolved polymer by pouring thesupernatant THF into 150 m
31、L of cold methanol (5C) in a 400mL beaker and stir with a metal spatula for 5 minutes. Allowthe mixture to stand for another 5 min at 5C (for example, inan ice bath) to allow for the polymer to precipitate out ofsolution.11.1.6 Filter the polymer precipitate through a vacuumfunnel over No. 2 Whatman
32、 filter paper. Remove the polymerfrom the filter paper while it is still damp, and place thepolymer onto a watch-glass to dry the excess of THF in anoven at 65C for 15 minutes.11.1.7 Repeat 11.1.3 11.1.6 twice for a total of threeiterations to retain a polymer sample free of interference asdefined i
33、n Section 6.11.1.8 After three iterations as per 11.1.7, place the ex-tracted and purified polymer sample into a 20 mL sample vialand dry it free of THF by heating it to 60C for 8 hours undervacuum.D8154 172NOTE 3Thorough drying is required to remove traces of THF, whichwill interfere with the calcu
34、lated PVC-KEE content NMR analysis. THFwill be readily visible in the1H-NMR spectrum. Before dissolution of thesample in deuterated-THF as per 11.2.1, the absence of protonated-THFmay be verified by means of Fourier-transform infrared spectroscopy, orthermo-gravimetric analysis.11.1.9 Reserve the po
35、lymer dried as per 11.1.8 in a flask toprotect it from contaminant until it is used to prepare the NMRsample.11.2 Preparation of NMR Sample:11.2.1 Polymer SampleWeigh in a small weighing panand with a precision of 0.001 mg about 20 mg of TCNB andabout 30 mg of polymer dried as per 11.1.8. Transfer t
36、hesesolids toa5mLweighting glass bottle. Use about 1 mL ofTHF-d8to wash residual solid in the weighting pan and pipetit out to the glass bottle. Close the weighing glass bottle withits lid, and leave the polymer-TCNB solid mixture to dissolveovernight. With a pipette, transfer the solution intoa5mmN
37、MR tube.NOTE 4Keep aside the weights of TCNB and the dried polymer foruse in the calculation of PVC and KEE content in Section 13.11.2.2 Calibration SamplesCalibration samples havePVC/KEE weight ratios close to 20/80, 30/70, 40/60, 50/50,and 60/40. Samples are prepared by individually weightingbetwe
38、en about 5 mg to 25 mg of PVC and KEE for a totalpolymer content near 30 mg. Weigh in a small weighing panand with a precision of 0.001 mg about 20 mg of TCNB andabout 30 mg of the PVC/KEE mixture with a set ratio. Transferthese solids toa5mLweighting glass bottle. Use about 1 mLofTHF-d8to wash resi
39、dual solid in the weighting pan and pipetit out to the weighing bottle. Close the weighing bottle with itslid, and leave the polymer-TCNB solid mixture to dissolveovernight. With a pipette, transfer the solution intoa5mmNMR tube. Table X1.1 in Appendix X1 provides an example ofcalibration sample com
40、positions.NOTE 5Keep aside the weights of TCNB, PVC, and KEE for use inthe calibration curve and calculation of PVC and KEE as per 13.1.2.12. NMR Analysis12.1 Acquisition ParametersThe proton-NMR probe tem-perature is to be set to 30C and sample is to be left to stabilizefor 20 minutes in the probe
41、prior to testing. Measure spin-lattice relaxation, T1, by inversion recovery. Set the relaxationdelay to about six times the value of T1to ascertain that fullrelaxation is achieved in the quantitative experiment. Forinstance, a 60 s relaxation delay is used for a T1of 9.9 s.NOTE 6Probe tuning and 90
42、 degree pulse width determination mustbe done for every sample prior to acquisition, for example 9.3 s at 53 dB.12.1.1 Collect the quantitative1H-NMR spectrum at aspectral width of 8.0 kHz, acquisition time of 3.75 s, andco-add 32 scans (transients).12.2 Spectrum AnalysisReference the spectrum at 3.
43、570ppm with respect to the proton trace inTHF-d8. Upon spectrumprocessing as per 12.3, set to 100 the integral regions from 7.80to 8.40 ppm for TCNB, and obtain the integration from 4.12 to4.75 ppm for PVC. Fig. X1.1 in Appendix X1 provides anexample of a spectrum with integration.12.3 Spectrum Proc
44、essingFor quantitative NMR, thepeaks must be as narrow and symmetric as possible and theintegral line must reflect the surface area of spectral lines aswell as the absence of spectral lines (flat baseline). Note, forinstance, the flat baseline on the TCNB integration in Fig.X1.1.12.3.1 PhasingIt is
45、first necessary to greatly expand thevertical scale of the spectrum to see the base of the peaks andmake them as symmetric as possible by adjusting the phase sothat the tails on each side of the peaks are as short andsymmetric as possible. Phasing is done by adjusting twoparameters: the zero order a
46、nd the first order phase and theprocess vary depending on the NMR software.12.3.2 IntegrationOnce properly phased, the spectrummust be processed for baseline correction for the integral lineto reflect the baseline; the integral line should increase when apeak is present and should be flat in the abs
47、ence of peaks. Onceagain, the process is different depending on the software usedfor data processing, but it is similar to phasing in the sense thata zero and first order parameter must be adjusted.13. KEE Calculations13.1 Two methods may be used to quantify the ratio of KEEand PVC in the extracted
48、polymer blend. Both methods arebased on the NMR integration values of peaks from the internalstandard TCNB and PVC. In Method A, the polymer ratio isobtained from the analysis of a single sample. In Method B, thepolymer ratio is obtained after the development of a calibrationcurve.NOTE 7The TCNB sig
49、nal between 7.80 to 8.40 ppm arises from asingle proton, and it is assumed that the PVC signal between 4.12 to 4.75ppm also arises from a single proton, from CH2-CHCl.13.1.1 Method A.13.1.1.1 Calculation of PVC ContentIn this method, thepolymer and TCNB weights from 11.2.1, and the NMRintegration values from TCNB and PVC in 12.2 are used tocalculate the PVC weight content as per Eq 1, where MWis themolecular weight. The MW of TCNB is 260.89 g/mol, whereasthat of PVC is 62.50 g/mol.PVC content % 5 100*PVC masssample mass(1)5100*molar quantity PVC
