1、Designation: D 4773 02 (Reapproved 2007)Standard Test Method forPurity of Propylene Glycol Monomethyl Ether, DipropyleneGlycol Monomethyl Ether, and Propylene GlycolMonomethyl Ether Acetate1This standard is issued under the fixed designation D 4773; the number immediately following the designation i
2、ndicates the year 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 (e) indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers the determina
3、tion by gaschromatography of propylene glycol monomethyl ether (PM),dipropylene glycol monomethyl ether (DPM), and propyleneglycol monomethyl ether acetate (PMA).NOTE 1Propylene glycol monomethyl ether (PM) is a mixture of twoisomers: 1-methoxy-2-propanol and 2-methoxy-1-propanol.Dipropylene glycol
4、monomethyl ether (DPM) is a mixture of fourisomers: 1-(2-methoxy-1-methylethoxy)-2-propanol is one of the majorisomers.Propylene glycol monomethyl ether acetate (PMA) is a mixture of twoisomers: 1-methoxy-2-acetoxypropane and 2-methoxy-1-acetoxypropane.1.1.1 This test method covers the determination
5、 of PM inthe range from 98 to 100 %, and DPM in the range from 0.08to 0.6 %.1.1.2 This test method covers the determination of DPM inthe range from 98 to 100 %, PM in the range from 0.05 to0.3 %, and tripropylene glycol monomethyl ether (TPM) in therange from 0.06 to 0.3 %.1.1.3 This test method cov
6、ers the determination of PMA inthe range from 99 to 100 %, and PM in the range from 0.03 to1.0 %.1.2 Water and acid cannot be determined by this test methodand must be measured in accordance with Test MethodsD 1364 and D 1613, and the results used to normalize thechromatographic data.1.3 The followi
7、ng applies to all specified limits in thisstandard; for purposes of determining conformance with thisstandard, an observed value or a calculated value shall berounded off “to the nearest unit” in the last right-hand digitused in expressing the specification limit, in accordance withthe rounding-off
8、method of Practice E29.1.4 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.5 For hazard information and guidance, see the suppliersMaterial Safety Data Sheet.1.6 This standard does not purport to address all of thesafety conce
9、rns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 1364 Test Method for Water in Volatile
10、 Solvents (KarlFischer Reagent Titration Method)D 1613 Test Method for Acidity in Volatile Solvents andChemical Intermediates Used in Paint, Varnish, Lacquer,and Related ProductsE29 Practice for Using Significant Digits in Test Data toDetermine Conformance with Specifications3. Summary of Test Metho
11、d3.1 A representative sample of PM, DPM, or PMA contain-ing the appropriate internal standard is injected into a capillarygas chromatograph and the components are detected with aflame ionization detector. Quantification is made by peak areameasurement using internal standardization and a computingin
12、tegrator.4. Significance and Use4.1 This test method is used to determine the purity of PM,DPM, and PMAby subtracting calculated total impurities from100 %.4.2 This test method is used to determine the quantity ofresidual glycol ether present in PMA.4.3 This test method is used for identifying vario
13、us impu-rities in PM, DPM, and PMA.1This test method is under the jurisdiction of ASTM Committee D01 on Paintand Related Coatings, Materials, and Applications and is the direct responsibility ofSubcommittee D01.35 on Solvents, Plasticizers, and Chemical Intermediates.Current edition approved June 1,
14、 2007. Published June 2007. Originallyapproved in 1988. Last previous edition approved in 2002 as D 4773 02.2For 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 stan
15、dards Document Summary page onthe ASTM website.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5. Apparatus5.1 ChromatographAny programmed temperature gaschromatograph
16、 designed or modified for use with capillarycolumns. The chromatograph must also be equipped with aflame ionization detector.5.2 ColumnCapillary, 5 m thick film, 10 m by 0.32 mminside diameter, fused silica coated, with 5 % phenyl methylsilicon liquid phase.5.3 Syringe10 L or equivalent to introduce
17、 a represen-tative sample onto the column.5.4 Computing Integator, capable of peak summation and abaseline construction.5.5 Analytical Balance, capable of measuring 0.1 mg.6. Reagents and Materials6.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it
18、 is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.3Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its
19、use without lessening theaccuracy of the determination.6.2 Gases:6.2.1 Carrier GasHelium, with a minimum purity of99.95 mol % for use with a flame ionization detector.6.2.2 Detector GasHydrogen with a minimum purity andair for use with the flame ionization detector.6.3 Standards for Calibration and
20、Identification:6.3.1 N-Butyl AcetateDistilled-in-glass purity for use asan internal standard in determination of PMA.6.3.2 MonochlorobenzeneDistilled-in-glass purity for useas an internal standard in determination of PM and DPM.6.3.3 Dipropylene Glycol Monomethyl Ether (DPM)Purity should be determin
21、ed and the standard solution adjustedfor this purity.6.3.4 Propylene Glycol Monomethyl Ether (PM)Purityshould be determined and the standard solution adjusted forthis purity.6.3.5 Propylene Glycol Monomethyl Ether Acetate(PMA)Purity should be determined and the standard solutionadjusted for this pur
22、ity.6.3.6 Tripropylene Glycol Monomethyl Ether (TPM)Purity should be determined and the standard solution adjustedfor this purity.7. Calibration and Standardization7.1 Preparation of Calibration Standard Solution:7.1.1 Propylene Glycol Monomethyl Ether (PM)Weighinto a vial to within 0.1 mg, 10.00 g
23、of PM calibration standard(see 6.3.4) and 0.02 g of DPM. Check these reagents for purityunder the conditions used in the procedures and, if interferingcompounds are present, adjustment must be made in preparingthe standard.7.1.2 Dipropylene Glycol Monomethyl Ether (DPM)Weigh into a vial to within 0.
24、1 mg, 10.00 g of DPM calibrationstandard (see 6.3.3), 0.02 g of PM calibration standard (see6.3.4), and 0.02 g of TPM (see 6.3.6). Check these reagents forpurity under the conditions used in the procedure and, ifinterfering compounds are present, adjustment must be made inpreparing the standard.7.1.
25、3 Propylene Glycol Monomethyl Ether Acetate(PMA)Weigh into a vial to within 0.1 mg, 10.00 g of PMAcalibration standard (see 6.3.5) and 0.04 g of PM. Check thesereagents for purity under the conditions used in the procedureand, if interfering compounds are present, adjustment must bemade in preparing
26、 the standard.7.2 Preparation of Standard:7.2.1 Weigh into a vial to within 0.1 mg, 1.0 g of the desiredcalibration standard solution (see 7.1.1 for PM, 7.1.2 for DPMand 7.1.3 for PMA).7.2.2 Into the respective vials for PM and DPM, weigh towithin 0.1 mg, 1.0 g of monochlorobenzene internal standard
27、(see 6.3.2), tightly seal with a polyethylene-lined cap, and mixthoroughly.7.2.3 Into the vial containing PMA, weigh to within 0.1 mg,1.0gofn-butyl acetate internal standard (see 6.3.1), tightlyseal with a polyethylene lined cap, and mix thoroughly.7.3 Chromatographic Conditions:Column: capillary fu
28、sed silicaLength, m 10Inside diameter, mm 0.32Film thickness, m 5Injection temperature, C 300Detector temperature, C 300Split: 30:1Specimen size, L 0.5 needle flashOven temperature, C at 8C/min 80260Column flow, mL/min (He) 1.2Makeup flow, mL/min (He) 24Internal standard:PM DPM PMAMonochlorobenzene
29、monochlorobenzene n-butyl acetate7.4 Calibration for Propylene Glycol Monomethyl Ether(PM):7.4.1 Make a needle-flash injection of the standard into thechromatograph and separate according to the chromatographicconditions in 7.3. At the end of the run, set the peak summingwindows to sum the isomer pe
30、aks as shown in Areas I and IIof Fig. 1.7.4.2 Program the integrator to set the baseline at the sametime peak summation begins for the PM isomers. Force theintegrator to extend a baseline horizontally from the setbaseline.7.4.3 Make another needle-flash injection of the standardand calibrate the int
31、egrator according to the manufacturersoperating instruction for an internal standard method. Re-sponse factors should agree within the precision of this testmethod. If not, recalibrate and repeat the analysis.7.4.4 If manual calculations are used, calculate the responsefactors RF for each component
32、as follows:3“Reagent Chemicals, American Chemical Society Specifications,” AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see “Analar Standards for LaboratoryChemicals , BDH Ltd., Poole, Dorset, U.K., and the United St
33、ates Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D 4773 02 (2007)2RF 5 A 3 B!/C 3 D! (1)where:A = peak area of internal standard,B = component of interest in standard, g,C = peak area for component of interest in standard, andD = internal standard in
34、standard mixture, g.7.5 Calibration for Dipropylene Glycol Monomethyl Ether(DPM):7.5.1 Make a needle-flash injection of the standard into thechromatograph and separate according to the chromatographicconditions in 7.3. At the end of the run, set the peak summingwindows to sum the PM, DPM, and TPM is
35、omer peaks asshown in Areas I, II, and III, respectively, of Fig. 2.7.5.2 Program the integrator to set the baseline at the sametime peak summation begins for the DPM isomers. Force theintegrator to extend a baseline horizontally from the setbaseline for the DPM isomer peaks.7.5.3 Make another needl
36、e-flash injection of the standardand calibrate the integrator according to the manufacturersoperating instruction for an internal standard method. Re-sponse factors should agree within the precision of this testmethod. If not, recalibrate and repeat the analysis.7.5.4 If manual calculations are used
37、, calculate the responsefactors RF for each component as follows:RF 5 A 3 B!/C 3 D! (2)where:A = peak area of internal standard,B = component of interest in standard, g,C = peak area for component of interest in standard, andD = internal standard in standard mixture, g.7.6 Calibration for Propylene
38、Glycol Monomethyl EtherAcetate (PMA):7.6.1 Make a needle-flash injection of the standard into thechromatograph and separate according to the chromatographicconditions in 7.3. At the end of the run, set the peak summingwindows to sum the PM and PMA isomer peaks as shown inAreas I and II, respectively
39、, of Fig. 3.7.6.2 Program the integrator to set the baseline at the sametime peak summation begins for the PMA isomers. Force theintegrator to extend a baseline horizontally from the setbaseline.7.6.3 Program the integrator to set the baseline and force abaseline horizontally prior to the elution of
40、 the PM peak.7.6.4 Make another needle-flash injection of the standardand calibrate the integrator according to the manufacturersoperating instruction for an internal standard method. Re-sponse factors should agree within the precision of this testmethod. If not, recalibrate and repeat the analysis.
41、7.6.5 If manual calculations are used, calculate the responsefactors RF for each component as follows:RF 5 A 3 B!/C 3 D! (3)where:A = peak area of internal standard,B = component of interest in standard, g,C = peak area for component of interest in standard, andD = internal standard in standard mixt
42、ure, g.8. Procedure8.1 Weigh 1.0 g of the specimen to the nearest 0.1 mg intoa vial.8.2 Into the same vial, weigh 1.0 g of the appropriateinternal standard (see 6.3.1 for PMA and 6.3.2 for PM andDPM). Tightly close with a polyethylene-lined cap and mixthoroughly.8.3 Enter internal standard and speci
43、men weight into theintegrator.FIG. 1 Chromatographic Data for PMFIG. 2 Chromatographic Data for DPM FIG. 3 Chromatographic Data For PMAD 4773 02 (2007)38.4 Make a needle-flash injection into the chromatographand separate according to the conditions in 7.3.9. Calculation9.1 Total Weight Percent Impur
44、ities The response factorsof the standardized impurities are used to calculate the totalweight percent of all detected organic impurities.9.1.1 Calculate the total weight percent impurities in PMusing the response factor determined for DPM (see 7.4).9.1.2 Calculate the total weight percent impuritie
45、s in DPMusing the response factor determined for PM for componentswith a retention time before DPM, and using the responsefactor determined for TPM for components with a retentiontime after DPM (see 7.5).9.1.3 Calculate the total weight percent impurities in PMAusing the response factor determined f
46、or PM (see 7.6).NOTE 2Peak areas may be determined by any method that meets theprecision limits given in Section 11. Electronic integration of peak areaswas employed to obtain the results used to establish the precision of thistest method.9.2 Weight Percent AssayCalculate the weight percentassay, W,
47、 as follows:W 5 100 2 A 1 B! (4)where:A = total weight percent impurities andB = sum of percent water and acidity.10. Report10.1 Report the following information:10.1.1 The adjusted percent of the component of interest ascalculated in Section 9 and10.1.2 The water and acid present in the specimen as
48、calculated in accordance with Test Methods D 1364 andD 1613.11. Precision and Bias11.1 An interlaboratory study of this test method in whichseven operators in seven laboratories analyzed four specimensof each product is the basis for the following:11.1.1 Propylene Glycol Monomethyl Ether (PM)Materia
49、ls containing 98.3 to 99.4 % PM and 0.09 to 0.42 %DPM had a within-laboratory standard deviation of 0.015 forDPM with 1 df and the between-laboratory standard deviationwas found to be 0.06 for DPM with 13 df. Based on thesestandard deviations, the following criteria should be used forjudging the acceptability of results at the 95 % confidencelevel:11.1.1.1 RepeatabilityTwo results, each the mean of du-plicates by the same operator, should be considered suspect ifthey differ by more than 0.016 for DPM.11.1.1.2 ReproducibilityTwo results, eac
