1、Designation: E1090 08Standard Test Method forDicumyl Peroxide and Dicumyl Peroxide DecompositionProducts in Resins1This standard is issued under the fixed designation E1090; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year
2、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 covers and is applicable to the deter-mination of dicumyl peroxide2and the decomposition products
3、dimethylbenzyl alcohol and acetophenone in cured and un-cured polyethylene (PE) and ethylene vinyl acetate (EVA)resins. These uncured polymers normally contain from 1 to 2 %dicumyl peroxide, whereas the residual peroxide level in thecured polymers is usually less than 0.1 %.1.2 The values stated in
4、SI units are to be regarded asstandard. The values given in parentheses are for informationonly.1.3 Review the current Material Safety Data Sheets (MSDS)for detailed information concerning toxicity, first aidprocedures, and safety precautions.1.4 This standard does not purport to address all of thes
5、afety 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-bility of regulatory limitations prior to use. Specific hazards aregiven in Section 7.2. Referenced Documents2.1 ASTM
6、Standards:3D1193 Specification for Reagent WaterE180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial and Spe-cialty Chemicals (Withdrawn 2009)4E300 Practice for Sampling Industrial ChemicalsE682 Practice for Liquid Chromatography Terms and Rela-tionshipsE
7、685 Practice for Testing Fixed-Wavelength PhotometricDetectors Used in Liquid ChromatographyE755 Test Method for Dicumyl Peroxide, Assay (LiquidChromatography)3. Summary of Test Method3.1 Dicumyl peroxide and dimethylbenzyl alcohol are ex-tracted from a cryogenically ground sample with methylenechlo
8、ride. The extract is concentrated, redissolved in methanol,and analyzed by high performance liquid chromatography(HPLC). Acetophenone is extracted from a separate samplewith methanol and analyzed directly by HPLC. The analysesare performed on a reversed phase octadecylsilane (ODS)column using aceton
9、itrile/water as the mobile phase and anultraviolet detector at 254 nm. The concentration of eachcomponent is determined by the internal standard technique,using peak height ratios of the sample and standard chromato-grams.4. Significance and Use4.1 Knowledge of the peroxide content of uncured PE and
10、EVA samples is required to regulate the degree of crosslinkingin the cured product. As end use applications of the curedproduct can be affected by residual amounts of the peroxide orits decomposition productsdimethylbenzyl alcohol andacetophenoneknowledge of these levels is also important.This test
11、method provides a procedure for determining theconcentration of these compounds. A method for the HPLCassay of dicumyl peroxide is described in Test Method E755.5. Apparatus5.1 Liquid Chromatograph, equipped with a 254-nm UVdetector, injection valve, and an isocratic-solvent deliverysystem capable o
12、f operating to a gage pressure of 3000 psi. Thedetector should be equipped with an attenuator switch tochange the sensitivity range as required. (See Practices E682and E685.)5.2 Recorder, 0 to 1 mv range,1sorless full-scaledeflection, with a chart speed of 0.1 in./min or other convenient1This test m
13、ethod is under the jurisdiction of ASTM Committee D16 onAromatic Hydrocarbons and Related Chemicals and is the direct responsibility ofSubcommittee D16.15 on Industrial and Specialty General Standards.Current edition approved April 1, 2008. Published May 2008. Originallyapproved in 1986. Last previo
14、us edition approved in 2002 as E1090 96 (2002).DOI: 10.1520/E1090-08.2Dicumyl peroxide; peroxide, bis(1-methyl-1-phenylethyl) C18H22O2; CASRegistry No. 80-43-3.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of
15、 ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.4The last approved version of this historical standard is referenced onwww.astm.org.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive,
16、 PO Box C700, West Conshohocken, PA 19428-2959. United StatesNOTICE: This standard has either been superseded and replaced by a new version or withdrawn.Contact ASTM International (www.astm.org) for the latest information1speed that will produce a satisfactory chromatogram. As analternative, an elec
17、tronic data system can be used.5.3 Chromatographic Column, reversed phase C-18, from250 to 300-mm by 3.9-mm inside diameter, containing octa-decylsilane chemically bonded to microparticulate silica.5NOTE 1Commercial HPLC columns may vary in physicaldimensions, degree of substrate loading, and size a
18、nd type of supportmaterial. For these reasons, some modification in the operating parametersmay be required to achieve optimum separation.5.4 Guard Column, reversed phase C-18, containing octa-decylsilane chemically bonded to microparticulate silica.5.5 Filter Funnel, Buchner, 60-mL capacity, with m
19、ediumporosity glass frit.5.6 Vials, screw cap, 4-dram and 1-dram capacities, withPTFE-lined caps.5.7 Freezer Mill, for pulverizing samples at liquid nitrogentemperature.6,75.8 Bottles, screw cap, wide-mouth, 2-oz capacity, withPTFE-lined caps.5.9 Sample Filter, consisting of a syringe and 0.45-m fil
20、terassembly to remove microparticulate matter from the preparedsample solution.7,85.10 Tube, borosilicate glass, approximately 8-in. long by1-in. diameter with tapered end, for warming cryogenicallyground resin samples to ambient temperature (see Fig. 1).5.11 Solvent Evaporation AssemblySee Fig. 2.5
21、.12 Silica Gel Purification Column.7,96. Reagents6.1 Methanol, chromatographic grade, distilled in glass.6.2 Acetonitrile, chromatographic grade, distilled in glass.6.3 Water, prepare Type II reagent water in accordance withSpecification D1193, or distill deionized water. Filter through a0.45-m filt
22、er7,10and store in a glass container.6.4 Acetonitrile:Water, 70:30Mix 7 volumes of acetoni-trile with 3 volumes of water.6.5 Acetonitrile:Water, 30:70Mix 3 volumes of acetoni-trile with 7 volumes of water.6.6 Acetonitrile:Water, 95:5Mix 9.5 volumes of acetoni-trile with 0.5 volumes of water.6.7 Meth
23、ylene Chloride, chromatographic grade, distilled inglass.6.8 Dibutyl Phthalate, purified.7,116.9 Dibutyl Phthalate Internal Standard (approximately 7.0mg/mL)Weigh 7.0 6 0.1 g of dibutyl phthalate to the nearest0.1 mg. Dissolve in methanol and quantitatively transfer to a1-L volumetric flask. Dilute
24、to volume with methanol and mixthoroughly. Calculate the exact concentration of dibutyl phtha-late.6.9.1 Long-term storage of a methanolic solution of dibutylphthalate should be avoided. Dibutyl phthalate in the presenceof traces of acidic or basic impurities may transesterify. Iftransesterification
25、 occurs, the dibutyl phthalate peak willslowly decrease, and the appearance of the methylbutyl phtha-late peak (k1value about 3.8) will be noted.6.10 Dibutyl Phthalate Internal Standard (approximately0.7 mg/mL)Pipet 100 mL of dibutyl phthalate standard (6.9,approximately 7 mg/mL) into a 1-L volumetr
26、ic flask. Dilute tovolume with methanol and mix thoroughly. Calculate the exactconcentration of dibutyl phthalate.6.11 Benzyl Alcohol, purified.7,126.12 Benzyl Alcohol Internal Standard (approximately 15.0mg/mL)Weigh 15.0 6 0.1 g of benzyl alcohol to the nearest0.1 mg. Dissolve in methanol and quant
27、itatively transfer to a1-L volumetric flask. Dilute to volume with methanol and mixthoroughly. Calculate the exact concentration of benzyl alco-hol.6.13 Benzyl Alcohol Internal Standard (approximately 1.5mg/mL)Pipet 100 mL of benzyl alcohol standard (6.12,approximately 15 mg/mL) into a 1-Lvolumetric
28、 flask. Dilute tovolume with methanol and mix thoroughly. Calculate the exactconcentration of benzyl alcohol.6.14 Dicumyl Peroxide, RecrystallizedTransfer 25.0 g ofcommercial refined dicumyl peroxide into a 100-mL Erlen-meyer flask. Add 8.0 mL of methanol and gently warm the5Satisfactory results wer
29、e obtained using Waters -Bondapak C-18 (Cat. No.27324) and Waters Radial PAK C-18 (Cat. No. 84720) columns in a round-robinevaluation of the test method. Available from Waters Corporation, 34 Maple St.,Milford, MA 01757. Equivalent results should be obtainable with other commercialC-18 reversed phas
30、e columns.6The sole source of supply of the apparatus known to the committee at this timeis Spex Freezer/Mill, Catalog No. 6700, available from SPEX CertiPrep, 203Norcross Ave., Metuchen, NJ 08840, .7If you are aware of alternative suppliers, please provide this information toASTM International Head
31、quarters. Your comments will receive careful consider-ation at a meeting of the responsible technical committee,1which you may attend.8The sole source of supply of the apparatus known to the committee at this timeis Waters Associations Sample Clarification Kit, Catalog No. 26870, available fromWater
32、s Corporation, 34 Maple St., Milford, MA 01757.9The sole source of supply of the apparatus known to the committee at this timeis SEP-PAK silica gel cartridges, Waters No. 51-900, available from WatersCorporation, 34 Maple St., Milford, MA 01757.10The sole source of supply of the apparatus known to t
33、he committee at this timeis a 0.45-m Millipore type HA filter, available from Millipore retail locations(Millipore Corporate Headquarters, 290 Concord Road, Billerica, MA 01821,).11The sole source of supply of the apparatus known to the committee at this timeis Dibutyl phthalate, Aldrich Chemical Co
34、. No. 15243-9, available from AldrichChemical Company, Inc., 940 W. St. Paul Ave., Milwaukee, WI 53233-2625,.12The sole source of supply of the apparatus known to the committee at this timeis Benzyl alcohol, No. B1620-8, available from Aldrich Chemical Company, Inc.,940 W. St. Paul Ave., Milwaukee,
35、WI 53233-2625, .FIG. 1 Tube for Warming Cryogenically Ground Resin Samples toAmbient TemperatureE1090 082solution in a water bath while swirling, to effect completesolution. Cool to 0C in an ice bath. Transfer the contents to amedium-porosity sintered glass crucible and vacuum filter.Allow air to pa
36、ss through the filter for 10 to 15 min, to dry theperoxide. Repeat the crystallization twice using approximately1 mL of methanol for every3gofperoxide. Place therecrystallized dicumyl peroxide in a tightly capped bottle andstore in the refrigerator. Cautionsee Section 7.6.15 Acetophenone, purified.7
37、,136.16 ,-Dimethylbenzyl Alcohol (DMBA)Dissolve 0.2 gof ,-dimethylbenzyl alcohol7,14in2mLof98:2n-hexane:chloroform. Transfer the solution into a 5-mL syringeand carefully pass the solution through a SEP-PAK silica gelcartridge. Discard the eluate. Wash the column with anadditional 2 mLof 98:2 n-hexa
38、ne:chloroform and again discardthe eluate. Then, elute the DMBA with 5 mL of chloroform,collecting the eluate in a 50-mLfiltering flask. Stopper the flaskand attach the side arm to a water aspirator. Immerse the flaskin a water bath maintained at 35 to 40C until the chloroformhas completely volatili
39、zed. Store the purified DMBA in asealed vial.7. Hazards7.1 Organic peroxides are strong oxidizing agents andpresent potential fire and explosion hazards. Reactivity varieswidely and some compounds may explode when shocked.While dicumyl peroxide is one of the more stable peroxides,contact with reduci
40、ng agents and sources of heat, sparks, oropen flame must be avoided. Organic peroxides in general areirritating to the skin, eyes, and mucous membranes. Avoidbodily contact and handle only in a well-ventilated area.7.2 Small quantities of solid or molten dicumyl peroxidecan be safely handled at temp
41、eratures up to 55C. Dicumylperoxide should not be heated above 55C as the rate ofperoxide decomposition rapidly increases with increasing tem-peratures above this point.7.3 Only a water bath that has been preheated to the desiredtemperature and removed from the heat source should be usedfor warming
42、vessels containing dicumyl peroxide. Electricallyheated water baths should not be used as they may causelocalized hot spots. Other sources of heat considered unsafe forwarming containers of dicumyl peroxide include ovens, hotplates, and direct steam.13The sole source of supply of the apparatus known
43、 to the committee at this timeisAcetophenone, 99 %,Aldrich Chemical Co. No.A1,070-1, available fromAldrichChemical Company, Inc., 940 W. St. Paul Ave., Milwaukee, WI 53233-2625,.14The sole source of supply of the apparatus known to the committee at this timeis ,-Dimethylbenzyl alcohol, 99 %, Fluka C
44、hemical Corp. No. 78940, availablefrom Fluka Chemical Corp., 1001 W Saint Paul Ave., Milwaukee, WI 53233-2641,.FIG. 2 Solvent Evaporation Assembly for Preventing Accumulation and Loss of Volatile CompoundsE1090 0838. Sample Preparation8.1 Obtain at least3gofarepresentative sample and reducethe parti
45、cle size, if required, to approximately18 in. or lessusing stainless-steel shears. (See Practice E300.)8.2 Charge the stainless-steel sample vial with approxi-mately 1.5 g of sample, add the stainless-steel impactor rod,and cap the vial with the stainless-steel cover head.8.3 Carefully position the
46、vial in the freezer/mill which hasbeen precooled and filled with liquid nitrogen to the properlevel.8.4 Cool for 4 to 5 min, then activate the impactor and allowto pulverize for 3 to 4 min at optimum impactor rate. Consultmanufacturers instructions for detailed operating procedure.6,78.5 Remove the
47、sample vial and immediately place in aborosilicate tube through which a flow of dry air or nitrogen ismaintained. See Fig. 1. Allow to warm to ambient temperatureunder the dry air or nitrogen flow in order to excludeatmospheric moisture.8.6 Remove the pulverized sample and store in a clean,capped vi
48、al.8.7 Repeat 8.2 8.5 and combine with the pulverizedproduct obtained in 8.6. Reserve for extraction and HPLCanalysis.9. Procedure9.1 Preparation of Sample for Determination of DicumylPeroxide and Dimethylbenzyl Alcohol:9.1.1 Weigh a 2.0 6 0.1-g sample of cryogenically groundresin to the nearest 0.1
49、 mg and transfer to a 2-oz bottleequipped with a PTFE-lined screw cap.9.1.2 Add approximately 30 mL of methylene chloride, cap,and shake. Allow to stand at ambient temperature for 18 h withoccasional shaking to complete the extraction.9.1.3 Filter through a medium porosity sintered-glass filtercollecting the filtrate in a 125-mL filter flask. Rinse the resinwith several small portions of methylene chloride, collectingthe was
