1、Designation: D 7210 06Standard Practice forExtraction of Additives in Polyolefin Plastics1This standard is issued under the fixed designation D 7210; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A numb
2、er in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This practice covers a variety of extraction techniquesfor antioxidant and slip additives used in polyolefins. Typically,the extracted add
3、itives are separated and quantified using achromatographic technique such as the procedure explained inTest Method D 6953. Chromatographic analysis of the extractsis not included in this practice.1.2 This standard does not purport to address all of thesafety concerns, if any, associated with its use
4、. 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.NOTE 1There is no known ISO equivalent to this standard.2. Referenced Documents2.1 ASTM Standards:2D 883 Terminology Re
5、lating to PlasticsD 1600 Terminology for Abbreviated Terms Relating toPlasticsD 6953 Test Method for Determination of Antioxidants andErucamide Slip Additives in Polyethylene Using LiquidChromatography (LC)E 131 Terminology Relating to Molecular Spectroscopy3. Terminology3.1 Definitions:3.1.1 For de
6、finitions of plastic terms used in this practice,see Terminologies D 883 and D 1600.3.2 For units, symbols, and abbreviations used in thispractice refer to Terminology E 131.3.3 Abbreviations:3.3.1 LDPELow-Density Polyethylene3.3.2 LLDPELinear Low-Density Polyethylene3.3.3 HDPEHigh-Density Polyethyl
7、ene3.3.4 PPPolypropylene3.4 Definitions: Additives:3.4.1 BHEB2,6-di-t-butyl-4-ethyl-phenol or butylated hy-droxyethyl benzene, CAS No. 4130-42-13.4.2 BHT2,6-di-t-butyl-cresol or butylated hydroxytolu-ene, CAS No. 128-37-03.4.3 2-benzotriazol-2-yl-4-methylphenol, CAS No. 2440-22-43.4.4 bis(3,3,5,5-te
8、tramethyl-4-piperidyl)decanedioate,CAS No. 91450-21-43.4.5 Cis-13-docosenamide or erucamide slip, CAS No.112-84-53.4.6 N,N-diphenylbenzene-1,4-diamine, CAS No. 74-31-73.4.7 2,2-ethylidene bis (4,6-di-t-butyl phenol), CAS No.112-84-53.4.8 Tetrakismethylene (3,5-di-t-butyl-4-hydroxy hydro-cinnamate) m
9、ethane, CAS No. 98584-37-33.4.9 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, CAS No. 99346-90-43.4.10 Octadecyl-3,5-di-t-butyl-4-hydroxy hydrocinnamate,CAS No. 2082-79-33.4.11 Sodium Alkyl Sulfonate, CAS No. 68411-30-33.4.12 Tris(2,4-di-t-butylphenyl) phosphite, CAS No.31570-
10、04-43.4.13 Tris(2,4-di-t-butylphenyl) phosphate (oxidizedTris(2,4-di-t-butylphenyl) phosphite)3.4.14 TNPPTris(nonylphenyl) phosphite, CAS No.26523-78-43.4.15 Hydrolyzed TNPPNonylphenol, CAS No. 104-40-53.4.16 Oxidized TNPPTris(nonylphenol)phosphate CASNo. 26569-53-94. Summary of Practice4.1 The poly
11、mer sample is ground to approximately a0.5-mm (40-mesh) or 1-mm (20-mesh) particle size andextracted by one of the techniques listed in this practice.5. Significance and Use5.1 Separation and identification of additives used in themanufacture of polyolefin plastics is necessary in order tocorrelate
12、performance properties with polymer composition.1This practice is under the jurisdiction ofASTM Committee D20 on Plastics andis the direct responsibility of Subcommittee D20.70 on Analytical Methods.Current edition approved March 15, 2006. Published July 2006.2For referenced ASTM standards, visit th
13、e 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.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
14、United States.This practice provides guidelines for extracting phenolic anti-oxidants, phosphite antioxidants, UV stabilizers, antistaticagents, and slip additives, from milled polyolefin plastics .5.2 Water bath shakers and steam-reflux Soxhlet extractiontechniques have also been used to successful
15、ly remove addi-tives from polyolefin plastics.6. Interferences6.1 A major source of interferences can be from solventimpurities. For this reason, quality, high-grade solvents shouldbe used with this practice. It is recommended that solvents beexamined prior to use.6.1.1 Solvent evaporation after an
16、extraction technique canincrease the concentration of impurities.6.2 The milling or grinding process may cause a low bias.For example, some erucamide slip is known to be lost duringmilling. Excessive grinding may cause degradation of someantioxidant additives.6.3 Excessive fillers (for example, pigm
17、ents, talc, etc.) inthe polymer formulation can mask the sensitivity of polymeradditive detection.7. Apparatus7.1 Wiley Mill, or equivalent, equipped with a 20-meshscreen and water-cooled jacket to prevent the thermodegrada-tion of antioxidants such as BHT.NOTE 2ASPEX Certiprep, 6750 Freezer Mill us
18、ing liquid nitrogen asa coolant has also been used to successfully prepare milled polyolefinsamples.7.2 Extraction Apparatus7.2.1 Reflux-Extraction Apparatus, consisting of a con-denser (24/40 ground-glass joint), a flat bottom 125-mL flaskhaving a 24/40 ground glass joint, and a hot plate withmagne
19、tic stirrer.7.2.2 Soxhlet Apparatus, consisting of a Soxhlet extractiontube (24/40 ground-glass joint at bottom and a 34/45 ground-glass joint at top), an Allihn condenser (34/45 ground-glassjoint), a flat bottom 125-mL flask having a 24/40 ground-glassjoint, and a hot plate with magnetic stirrer. S
20、oxtec Solventextraction systems or equivalent devices may also be used.7.2.3 Accelerated Solvent Extractor (ASE) Apparatus3,4,5,equipped with 11-mL extraction cells and a solvent controller(optional) or equivalent.7.2.4 Microwave Extraction Apparatus (MAE)5,6, equippedwith 100-mL extraction vessels
21、or equivalent.7.2.5 Sonication Extraction Apparatus, consisting of a suit-able ultrasonic cleaner such as an Aquasonic Model 75DUltrasonic Cleaner or equivalent.7.3 Filter System, for nonaqueous solutions (pore size of0.22 m to 0.5m).7.4 Analytical Balance, capable of weighing to 60.0001 g.8. Reagen
22、ts and Materials8.1 Cellulose Extraction Thimble16mmby60mm,single thickness for use with Soxhlet apparatus.8.2 Cellulose Extraction Thimble17by19by37mm,foruse in the ASE system.8.3 Microwave Extraction Vessels100-mL extraction ves-sel.NOTE 311-mL extraction cells were used to evaluate the ASE portio
23、nof this practice and 100-mL extraction vessels were used to evaluate theMAE portion of this practice.8.4 Cyclohexane, optima grade, spectroquality, or chroma-tography quality reagent.8.5 Isobutanol, optima grade, spectroquality, or chromatog-raphy quality reagent.8.6 2-Propanol or Isopropanol, opti
24、ma grade, spectroqual-ity, or chromatography quality reagent.8.7 Methylene Chloride, optima grade, spectroquality orchromatography quality reagent.9. Safety Precautions9.1 Isopropanol, isobutanol, and cyclohexane are flam-mable. The extraction cells used in the instruments should befree of leaks.9.2
25、 Accelerated solvent and microwave extraction systemsoperate at elevated temperatures and pressures. Follow allsafety precautions supplied by the instrument manufacturer.10. Sample Preparation10.1 Mill the sample to a particle size of 1-mm or smallerusing a cooled Wiley Mill or another suitable grin
26、ding appa-ratus.10.2 Weigh 0.5 6 0.01 to 10.0 6 0.01 g of sample into theappropriate vessel (that is, flat-bottom flask for reflux extrac-tion procedures, cellulose extraction thimble for Soxhlet orASE extraction, or microwave vessel for MAE extraction, 8 ozglass jar for ultrasonic bath extraction).
27、 The required samplesize will vary from laboratory to laboratory and will depend onthe sensitivity of the analytical determinative method em-ployed.10.3 Depending on the extraction procedure chosen and thetype of polyolefin, or additive, or both, to be extracted, preparethe extraction solvent as fol
28、lows:10.3.1 Reflux or Soxhlet Extraction10.3.1.1 LDPE add 5.0 6 0.01 g of sample into the flask,add a stirring bar, accurately add 50.0 mL of a suitable solventsuch as 2-propanol and boil for 1 h (with stirring).10.3.1.2 LLDPE add 5.0 6 0.01 g of sample into the flask,add a stirring bar, accurately
29、add 50.0 mL of a suitable solventsuch as either isobutanol or 2-propanol and boil for 90 min(with stirring).10.3.1.3 HDPE add 5.0 6 0.01 g of sample into the flask,add a stirring bar, accurately add 50.0 mL of a suitable solventsuch as cyclohexane and boil for 1 h (with stirring).3The Accelerated So
30、lvent Extractor (ASE) Apparatus is a registered trademarkof Dionex Corporation.4The sole source of supply of the apparatus (ASE 200) known to the committeeat this time is Dionex Corporation, 1228 Titan Way, P.O. Box 3603, Sunnyvale, CA94088-3603, USA; www.D.5If you are aware of alternative suppliers
31、, please provide this information toASTM International Headquarters. Your comments will receive careful consider-ation at a meeting of the responsible technical committee,1which you may attend.6The sole source of supply of the microwave extraction apparatus (MARS-X)known to the committee at this tim
32、e is CEM Corporation, PO Box 200, Matthews,NC 28106-0200, USA; .D721006210.3.1.4 PP add 5.0 6 0.01 g of sample into the flask, adda stirring bar, accurately add 50.0 mL of a suitable solvent suchas methylene chloride: cyclohexane (75+25) and boil for 90min (with stirring).NOTE 4If internal standard
33、calibration is used with reflux or Soxhletextraction, add the internal standard to the extraction solvent at the start ofthe extraction procedure. If internal standard calibration is used withaccelerated solvent or microwave assisted extraction, add the internalstandard to the extraction vessel prio
34、r to initiating the extraction.NOTE 5If Soxhlet extraction is used, add the sample to the celluloseextraction thimble and place the thimble in the Soxhlet extraction tubebefore initiating the extraction.NOTE 6A suitable solvent is one that results in a quantitativeextraction of the additive(s) of in
35、terest.10.3.1.5 Cool the solution to room temperature by raisingthe flask off the hot plate while it is still attached to thecondenser.10.3.1.6 Analyze the extract using an appropriate chromato-graphic technique.10.3.2 Accelerated Solvent Extraction (refer to DionexApplication Note 331; www.D Insert
36、 a 17 by 19 by 37-mm cellulose extractionthimble into an 11-mL extraction cell.10.3.2.2 Weigh 0.5 6 0.001 g of the sample in a suitableweighing dish or in the extraction thimble. Add sample to anextraction cell that contains a cellulose extraction thimble orplace the cellulose extraction thimble con
37、taining the sample tobe extracted into the extraction cell.10.3.2.3 Place the cell in the upper carousel of the acceler-ated solvent extractor and place the appropriate number ofcollection vials in the lower carousel.10.3.2.4 Enter the following extraction conditions into theaccelerated solvent syst
38、em and initiate the run.(1) Oven Temperature120C.(2) Pressure1500 psi (10.34 MPa).(3) Solvent5 % cyclohexane in 2-propanol or a suitablesolvent (mixtures of acetonitrile and cyclohexane (95+5) andother solvent mixtures have also been found to be effectiveextraction solvents for this application).(4)
39、 Static Time3 min.(5) Flush Volume100 % (of cell volume).(6) Static Cycles3.(7) Purge Time60 s.10.3.2.5 At the completion of the extraction, remove thecollection vial containing the solvent extract from the lowercarousel.10.3.2.6 Analyze the extract using an appropriate chromato-graphic technique.10
40、.3.3 Microwave Accelerated Extraction (refer to CEMapplication notes E012 for HDPE, E017 for LDPE, and E020for LLDPE; Weigh approximately 1.5 g of sample to the nearest0.001 g into a 100-mL extraction vessel and add 20 mL of asuitable solvent. Slide the vessel into the supplied protectivesleeve and
41、 then into the support module. Using a torquewrench, tighten the cover screw to approximately 50 lb andplace the support module into the microwave carousel.10.3.3.2 Load the necessary extraction conditions into theMAE instrument and initiate the extraction. Typically, extrac-tions are performed at 3
42、0-50C above the boiling point of thesolvent for 15-30 min. Cool to well below the boiling point ofthe solvent before removing the vessels from the microwave.10.3.3.3 Analyze the extract using an appropriate chromato-graphic technique.10.3.4 Ultrasonic Extraction10.3.4.1 Weigh approximately 10.0 g of
43、 sample to thenearest 0.001 g and quantitatively transfer the sample into an 8oz tightly-sealed glass jar.Add 100 mL of suitable solvent suchas 75 % methylene chloride and 25 % cyclohexane to the jarcontaining the sample (toluene has also been successfully usedas an extraction solvent using this tec
44、hnique). Tightly seal thejar containing the sample and solvent mixture.10.3.4.2 Suspend the jar containing the sample and solventin an ultrasonic water bath. Turn on the ultrasonic bath for 2hours. The water temperature in the ultrasonic bath usuallyreaches about 50C during this extraction procedure
45、.NOTE 7Solvents expand when heated. Use caution during this pro-cedure. Make certain the glass jar is free from chips, cracks, and otherstructural deformities. The ultrasonic extraction conditions above are notapplicable for the extraction of Tetrakis methylene (3,5-di-t-butyl-4-hydroxy hydrocinnama
46、te) methane.NOTE 8Allow the glass jar used in the ultrasonic extraction to coolprior to transferring the extract into vials for analysis. Allowing the jar tocool for 20 to 30 minutes will minimize the possibility of a potentialchemical flash or “burp” when the jar is opened.10.3.4.3 Analyze the extr
47、act using an appropriate chromato-graphic technique.11. Precision and Bias11.1 These procedures are for sample preparation and assuch they depend on a determinative method to produce aresult.12. Keywords12.1 accelerated solvent extraction; antistatic agents;BHEB; BHT; high-density polyethylene (HDPE
48、); linear low-density polyethylene (LLDPE); low-density polyethylene(LDPE); microwave assisted extraction; phenolic antioxidants;phosphite antioxidants; polymer additive; polypropylene (PP);reflux extraction; slip additives; Soxhlet extraction; ultrasonicor sonication extraction; UV stabilizersD7210
49、063ASTM International takes no position 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.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 re
