1、Designation: D 4590 09Standard Test Method forColorimetric Determination of p-tert-Butylcatechol In StyreneMonomer or AMS (aMethylstyrene) by Spectrophotometry1This standard is issued under the fixed designation D 4590; the number immediately following the designation indicates the year oforiginal a
2、doption 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 is applicable to the determination ofresidual 4-ter
3、tiary-butylcatechol (TBC) in styrene monomer orAMS in the 1 to 100 ppm (mg/kg) range. Any other compoundproducing color at 490 nm when contacted with aqueoussodium hydroxide solution will interfere. It may be compen-sated for by including it in the preparation of the standardsolutions, if its identi
4、ty and concentration in the sample areknown.1.2 In determining the conformance of the test results usingthis method to applicable specifications, results shall berounded off in accordance with the rounding-off method ofPractice E29.1.3 The values stated in SI units are to be regarded asstandard. No
5、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 determine the applica-bilit
6、y of regulatory limitations prior to use. For specificstatements on hazards, see Section 8.2. Referenced Documents2.1 ASTM Standards:2D 1193 Specification for Reagent WaterD 3437 Practice for Sampling and Handling Liquid CyclicProductsD 4790 Terminology of Aromatic Hydrocarbons and Re-lated Chemical
7、sD 6809 Guide for Quality Control and Quality AssuranceProcedures for Aromatic Hydrocarbons and Related Ma-terialsE29 Practice for Using Significant Digits in Test Data toDetermine Conformance with SpecificationsE 691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Te
8、st Method2.2 Other Document:OSHA Regulations, 29CFR paragraphs 1910.1000 and1910.120033. Terminology3.1 See Terminology D 4790 for definition of terms used inthis standard.4. Summary of Method4.1 Color is developed in the specimen by the addition ofcaustic in a methanol-octanol solvent. The intensit
9、y of the pinkcolor is measured with a spectrometer and compared to acalibration curve for quantitation.5. Significance and Use5.1 This test method is suitable for determining the quantityof TBC inhibitor, both for the protection against polymeriza-tion while in transit and storage, and for internal
10、qualitycontrol.6. Apparatus6.1 Visible Range Spectrometer, equipped with absorptioncells providing light paths from 1 to 5 cm for use at approxi-mately 490 nm.6.2 Volumetric Pipets and PipetorsThe sample pipet vol-ume should be sized to fill the spectrometer absorption cell.Pipetor volumes must be s
11、caled to the sample volume. Thisprocedure is written using a 15 mL sample volume. Thefollowing table shows how reagent pipetor volumes could bescaled to usea5mLsample volume.1This test method is under the jurisdiction of ASTM Committee D16 onAromatic Hydrocarbons and Related Chemicals and is the dir
12、ect responsibility ofSubcommittee D16.07 on Styrene, Ethylbenzene and C9and C10Aromatic Hydro-carbons.Current edition approved June 1, 2009. Published July 2009. Originally approvedin 1986. Last previous edition approved in 2006 as D 4590 06.2For referenced ASTM standards, visit the ASTM website, ww
13、w.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.3Available from U.S. Government Printing Office Superintendent of Documents,732 N. Capitol St., NW, Mail Stop: SDE, Was
14、hington, DC 20401, http:/www.access.gpo.gov.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.Sample Pipet,mL0.15 NaOH Pipetor,LMethanol Pipetor,L15 300 6005 100 2007. R
15、eagents and Materials7.1 Purity of ReagentsWhere unspecified, chemicals shallbe reagent grade and conform to recognized specifications ifsuch exist.4If found to have no adverse effect on accuracy,other grades may be used.7.2 4-Tertiary-Butylcatechol, Mp 52 to 55C.7.3 Toluene, ACS reagent grade.7.4 M
16、ethanol, reagent grade.7.5 n-Octanol, reagent grade.7.6 Aqueous Sodium Hydroxide, 10 Normal (10N), reagentgrade.7.7 Alcoholic Sodium Hydroxide, approximately 0.15 N.Mix 0.75 mL of 10N Aqueous Sodium Hydroxide with 25 mLmethanol. With stirring, add 25 mL of n-octanol and then 0.75mL of water. Store t
17、he reagent in an amber glass bottle. Thisreagent can be used immediately after preparation and is stablefor at least 2 months. To reduce exposure of the reagent to theatmosphere, transfer enough for several samples to a smallclean vial.7.8 TBC Stock StandardThis standard may be purchasedif desired.
18、Prepare a stock solution by weighing 0.500 6 0.001g of TBC to the nearest 0.0001 g into 500 6 1 g of toluene(weighed to the nearest 0.1 g). This solution will have aconcentration of approximately 1000 mg/kg TBC in tolueneand the exact concentration can be calculated using Eq 1. Thisstandard should h
19、ave a shelf life of one year or better if storedin a refrigerator or freezer. Storing standards in amber bottlessignificantly reduces degradation of standards with time.mg TBC / kg toluene 5 gofTBC! 3 Purity of TBC!3 106!# / g of toluene (1)7.9 Unless otherwise indicated, references to water shall b
20、eunderstood to mean any reagent water as defined in Specifica-tion D 1193.8. Hazards8.1 Consult current OSHA regulations, suppliers MaterialSafety Data Sheets, and local regulations for all materials usedin this test method.8.2 Handling Precautionsp-tert-butylcatechol, particu-larly when molten or i
21、n concentrated solution, is very corrosiveto the skin. It is also a systemic poison when taken orally orabsorbed in quantity through the skin.8.3 Flammable HazardsStyrene monomer is flammableand polymerizes exothermally in the presence of peroxide,mineral acids, and aluminum chloride.9. Sampling9.1
22、Collect the samples in accordance with Practice D 3437.10. Preparation of Calibration Curve10.1 Prepare standards of 5, 10, 20, 30, 40, 50, 70, and 100ppm (mg/kg) TBC in toluene by diluting 0.5, 1, 2, 3, 4, 5, 7,and 10 mLs of TBC stock standard to 100 mLs with toluene.NOTE 1Both the stock solution a
23、nd toluene diluent should be at roomtemperature. Temperature differences will cause dilution errors due tovariations in density.10.2 Determine the absorbance of each standard solutionand one reagent blank in accordance with Section 11.10.3 Plot absorbance versus concentration on standardgraph paper.
24、NOTE 2The plot should be close to a straight line. The maximumabsorbance should be within the absorbance range of the spectrometer. Ifnot, repeat the calibration with a spectrometer cell that has less pathlength.11. Procedure11.1 Zero the spectrometer with the specimen to be ana-lyzed.11.2 Add 15 mL
25、 of specimen to a clean round container.11.3 Verify that the alcoholic NaOH reagent and pipetor arefree of particulates.NOTE 3The particulates formed in the sodium hydroxide reagentfrom exposure to carbon dioxide in the atmosphere will scatter light andmay cause an error in the determination.11.4 Ad
26、d 300 L of alcoholic NaOH reagent to the con-tainer and mix vigorously with a vortex mixer for 30 s.NOTE 4If a vortex mixer is not available, continuous vigorousshaking for 30 s is required. Rapid reaction completion depends on theformulation of an emulsion of aqueous NaOH in the sample mixture.11.5
27、 Add 600 L of methanol to the container and shake forabout 15 s, creating a clear solution from the reaction emulsion.11.6 Measure the absorbance at 490 nm as soon as possibleand within 5 min.11.7 Read the concentration in parts per million TBC fromthe graph. Calculate the inhibitor content using Eq
28、 2 for densitycorrection:Inhibitor Content, mg/kg 5 Value from curve!3 toluene density!/sample density!#(2)12. Report12.1 Report the inhibitor content as parts per million (mg/kg) of p-tert-butylcatechol.13. Precision and Bias513.1 The interlaboratory study included six laboratoriesanalyzing three s
29、amples of unknown concentration of TBC andtwo determinations for each sample. Each determination wasthe result of one measurement as specified in this standard.Results of the interlaboratory study were calculated usingPractice E 691.4Reagent Chemicals, American Chemical Society Specifications, Ameri
30、canChemical 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 States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC
31、), Rockville,MD.5Supporting data are available from ASTM International Headquarters. RequestRR:D161009.D459009213.2 RepeatabilityResults in the same laboratory shouldnot be considered suspect unless they differ by more than thevalues shown in Table 1.13.3 ReproducibilityResults submitted by two labo
32、rato-ries should not be considered suspect unless they differ bymore than the values shown in Table 1.13.4 BiasThere is a bias associated with running the testmethod that is statistically significant at the 95 % confidencelevel. The bias for the unknown samples is an average absolutevalue of 0.6 mg/
33、kg with the observed results lower than theactual amounts added. However, at the 99 % confidence level,the bias is not statistically significant.14. Quality Guidelines14.1 Refer to Guide D 6809 for suggested QA/QC activitiesthat can be used as a part of this test method. It is recom-mended that the
34、operator of this test method select and performrelevant QA/QC activities like the ones in Guide D 6809 tohelp ensure the quality of data generated by this test method.15. Keywords15.1 alpha-methylstyrene; AMS; para-tertiary butyl cat-echol; PTBC; styrene, inhibitor content; styrene, TBC content;TBC
35、in styreneSUMMARY OF CHANGESCommittee D16 has identified the location of selected changes to this standard since the last issue(D 4590 - 06) that may impact the use of this standard. (Approved June 1, 2009.)(1) Revised instructions to prepare stock solution in 7.8.ASTM International takes no positio
36、n respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.
37、This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM I
38、nternational Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address sho
39、wn below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org).TABLE 1 Intermediate Precision and ReproducibilityTBC ObservedConcentrationRepeatability Reproducibility4.7 0.23 0.9415.2 0.47 5.0824.5 1.55 4.9194.6 3.98 9.94D4590093
