1、Designation: D7210 06D7210 13Standard Practice forExtraction of Additives in Polyolefin Plastics1This standard is issued under the fixed designation D7210; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision.
2、A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope Scope*1.1 This practice covers a variety of extraction techniques for antioxidant and slip additives used in polyolefins. Typically, the
3、extracted additives are separated and quantified using a chromatographic technique such as the procedure explained in Test MethodD6953. Chromatographic analysis of the extracts is not included in this practice.1.2 This standard does not purport to address all of the safety concerns, if any, associat
4、ed with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.NOTE 1There is no known ISO equivalent to this standard.2. Referenced Documents2.1 ASTM Standards:2D883 Ter
5、minology Relating to PlasticsD1600 Terminology for Abbreviated Terms Relating to PlasticsD6953 Test Method for Determination of Antioxidants and Erucamide Slip Additives in Polyethylene Using LiquidChromatography (LC)E131 Terminology Relating to Molecular Spectroscopy3. Terminology3.1 Definitions:3.
6、1.1 For definitions of plastic terms used in this practice, see Terminologies D883 and D1600.3.2 For units, symbols, and abbreviations used in this practice refer to Terminology E131.3.3 Abbreviations:3.3.1 LDPELow-Density Polyethylene3.3.2 LLDPELinear Low-Density Polyethylene3.3.3 HDPEHigh-Density
7、Polyethylene3.3.4 PPPolypropylene3.4 Definitions: Additives:3.4.1 BHEB2,6-di-t-butyl-4-ethyl-phenol or butylated hydroxyethyl benzene, CAS No. 4130-42-13.4.2 BHT2,6-di-t-butyl-cresol or butylated hydroxytoluene, CAS No. 128-37-03.4.3 2-benzotriazol-2-yl-4-methylphenol, CAS No. 2440-22-43.4.4 bis(3,3
8、,5,5-tetramethyl-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 hydrocin
9、namate) methane, CAS No. 98584-37-31 This practice is under the jurisdiction ofASTM Committee D20 on Plastics and is the direct responsibility of Subcommittee D20.70 on Analytical Methods. and SectionD20.70.01 on Physical Methods.Current edition approved March 15, 2006April 1, 2013. Published July 2
10、006April 2013. Originally approved in 2006. Last previous edition approved in 2006 as D7210 06. DOI: 10.1520/D7210-06.10.1520/D7210-13.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume info
11、rmation, refer to the standards Document Summary page on the ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately d
12、epict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary of Changes section appears at the end of this standardCopyright ASTM Internat
13、ional, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.4.9 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. 68
14、411-30-33.4.12 Tris(2,4-di-t-butylphenyl) phosphite, CAS No. 31570-04-43.4.13 Tris(2,4-di-t-butylphenyl) phosphate (oxidized Tris(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(nony
15、lphenol)phosphate CAS No. 26569-53-94. Summary of Practice4.1 The polymer sample is ground to approximately a 0.5-mm (40-mesh) or 1-mm (20-mesh) particle size and extracted byone of the techniques listed in this practice.5. Significance and Use5.1 Separation and identification of additives used in t
16、he manufacture of polyolefin plastics is necessary in order to correlateperformance properties with polymer composition. This practice provides guidelines for extracting phenolic antioxidants,phosphite antioxidants, UV stabilizers, antistatic agents, and slip additives, from milled polyolefin plasti
17、cs .5.2 Water bath shakers and steam-reflux Soxhlet extraction techniques have also been used to successfully remove additivesfrom polyolefin plastics.6. Interferences6.1 A major source of interferences can be from solvent impurities. For this reason, quality, high-grade solvents shouldshall beused
18、with this practice. It is recommended that solvents be examined prior to use.6.1.1 Solvent evaporation after an extraction technique can increase the concentration of impurities.6.2 The milling or grinding process may has the potential to cause a low bias. For example, some erucamide slip is known t
19、obe lost during milling. Excessive grinding maywill cause degradation of some antioxidant additives.6.3 Excessive fillers (for example, pigments, talc, etc.) in the polymer formulation can mask the sensitivity of polymer additivedetection.7. Apparatus7.1 Wiley Mill, or equivalent, equipped with a 20
20、-mesh screen and water-cooled jacket to prevent the thermodegradation ofantioxidants such as BHT.NOTE 2ASPEX Certiprep, 6750 Freezer Mill using liquid nitrogen as a coolant has also been used to successfully prepare milled polyolefin samples.7.2 Extraction Apparatus7.2.1 Reflux-Extraction Apparatus,
21、 consisting of a condenser (24/40 ground-glass joint), a flat bottom 125-mL flask having a24/40 ground glass joint, and a hot plate with magnetic stirrer.7.2.2 Soxhlet Apparatus, consisting of a Soxhlet extraction tube (24/40 ground-glass joint at bottom and a 34/45 ground-glassjoint at top), an All
22、ihn condenser (34/45 ground-glass joint), a flat bottom 125-mL flask having a 24/40 ground-glass joint, and ahot plate with magnetic stirrer. Soxtec Solvent extraction systems or equivalent devices may also be used.are also acceptable foruse.7.2.3 Accelerated Solvent Extractor (ASE) Apparatus3,4,5,
23、equipped with 11-mL extraction cells and a solvent controller(optional) or equivalent.7.2.4 Microwave Extraction Apparatus (MAE)5,6, equipped with 100-mL extraction vessels or equivalent.7.2.5 Sonication Extraction Apparatus, consisting of a suitable ultrasonic cleaner such as an Aquasonic Model 75D
24、 UltrasonicCleaner or equivalent.7.3 Filter System, for nonaqueous solutions (pore size of 0.22 m to 0.5m).7.4 Analytical Balance, capable of weighing to 60.0001 g.3 The Accelerated Solvent Extractor (ASE) Apparatus is a registered trademark of Dionex Corporation.4 The sole source of supply of the a
25、pparatus (ASE 200) known to the committee at this time is Dionex Thermo Fisher/Dionex Corporation, 1228 Titan Way, P.O. Box 3603,Sunnyvale, CA 94088-3603, USA; www.D.5 If you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will re
26、ceive careful consideration at ameeting of the responsible technical committee,1 which you may attend.6 The sole source of supply of the microwave extraction apparatus (MARS-X) known to the committee at this time is CEM Corporation, PO Box 200, Matthews, NC28106-0200, USA; .D7210 1328. Reagents and
27、Materials8.1 Cellulose Extraction Thimble16 mm by 60 mm, single thickness for use with Soxhlet apparatus.8.2 Cellulose Extraction Thimble17 by 19 by 37 mm, for use in the ASE system.8.3 Microwave Extraction Vessels100-mL extraction vessel.NOTE 311-mL extraction cells were used to evaluate the ASE po
28、rtion of this practice and 100-mL extraction vessels were used to evaluate the MAEportion of this practice.8.4 Cyclohexane, optima grade, spectroquality, or chromatography quality reagent.8.5 Isobutanol, optima grade, spectroquality, or chromatography quality reagent.8.6 2-Propanol or Isopropanol, o
29、ptima grade, spectroquality, or chromatography quality reagent.8.7 Methylene Chloride, optima grade, spectroquality or chromatography quality reagent.9. Safety Precautions9.1 Isopropanol, isobutanol, and cyclohexane are flammable. The extraction cells used in the instruments shouldshall be free ofle
30、aks.9.2 Accelerated solvent and microwave extraction systems operate at elevated temperatures and pressures. Follow all safetyprecautions supplied by the instrument manufacturer.10. Sample Preparation10.1 Mill the sample to a particle size of 1-mm or smaller using a cooled Wiley Mill or another suit
31、able grinding apparatus.10.2 Weigh 0.5 6 0.01 to 10.0 6 0.01 g of sample into the appropriate vessel (that is, flat-bottom flask for reflux extractionprocedures, cellulose extraction thimble for Soxhlet or ASE extraction, or microwave vessel for MAE extraction, 8 oz glass jarfor ultrasonic bath extr
32、action). The required sample size will vary from laboratory to laboratory and will depend on the sensitivityof the analytical determinative method employed.10.3 Depending on the extraction procedure chosen and the type of polyolefin, or additive, or both, to be extracted, prepare theextraction solve
33、nt as follows: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 solvent suchas 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,
34、accurately add 50.0 mL of a suitable solvent suchas 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 solvent suchas cyclohexane and boil for 1 h (with stirring).10.3.1
35、.4 PP add 5.0 6 0.01 g of sample into the flask, add a stirring bar, accurately add 50.0 mL of a suitable solvent such asmethylene chloride: cyclohexane (75+25) and boil for 90 min (with stirring).NOTE 4If internal standard calibration is used with reflux or Soxhlet extraction, add the internal stan
36、dard to the extraction solvent at the start of theextraction procedure. If internal standard calibration is used with accelerated solvent or microwave assisted extraction, add the internal standard to theextraction vessel prior to initiating the extraction.NOTE 5If Soxhlet extraction is used, add th
37、e sample to the cellulose extraction thimble and place the thimble in the Soxhlet extraction tube beforeinitiating the extraction.NOTE 6A suitable solvent is one that results in a quantitative extraction of the additive(s) of interest.10.3.1.5 Cool the solution to room temperature by raising the fla
38、sk off the hot plate while it is still attached to the condenser.10.3.1.6 Analyze the extract using an appropriate chromatographic technique.10.3.2 Accelerated Solvent Extraction (refer to Dionex Application Note 331; www.D Insert a 17 by 19 by 37-mm cellulose extraction thimble into an 11-mL extrac
39、tion cell.10.3.2.2 Weigh 0.560.001 g of the sample in a suitable weighing dish or in the extraction thimble.Add sample to an extractioncell that contains a cellulose extraction thimble or place the cellulose extraction thimble containing the sample to be extracted intothe extraction cell.10.3.2.3 Pl
40、ace the cell in the upper carousel of the accelerated solvent extractor and place the appropriate number of collectionvials in the lower carousel.10.3.2.4 Enter the following extraction conditions into the accelerated solvent system and initiate the run.(1) Oven Temperature120C.(2) Pressure1500 psi
41、(10.34 MPa).(3) Solvent5 % cyclohexane in 2-propanol or a suitable solvent (mixtures of acetonitrile and cyclohexane (95+5) and othersolvent mixtures have also been found to be effective extraction solvents for this application).(4) Static Time3 min.D7210 133(5) Flush Volume100 % (of cell volume).(6
42、) Static Cycles3.(7) Purge Time60 s.10.3.2.5 At the completion of the extraction, remove the collection vial containing the solvent extract from the lower carousel.10.3.2.6 Analyze the extract using an appropriate chromatographic technique.10.3.3 Microwave Accelerated Extraction (refer to CEM applic
43、ation notes E012 for HDPE, E017 for LDPE, and E020 forLLDPE; Weigh approximately 1.5 g of sample to the nearest 0.001 g into a 100-mLextraction vessel and add 20 mLof a suitablesolvent. Slide the vessel into the supplied protective sleeve and then into the support module. Using a torque wrench, tig
44、hten thecover screw to approximately 50 lb and place the support module into the microwave carousel.10.3.3.2 Load the necessary extraction conditions into the MAE instrument and initiate the extraction. Typically, extractions areperformed at 30-50C above the boiling point of the solvent for 15-30 mi
45、n. Cool to well below the boiling point of the solventbefore removing the vessels from the microwave.10.3.3.3 Analyze the extract using an appropriate chromatographic technique.10.3.4 Ultrasonic Extraction10.3.4.1 Weigh approximately 10.0 g of sample to the nearest 0.001 g and quantitatively transfe
46、r the sample into an 8 oztightly-sealed glass jar. Add 100 mL of suitable solvent such as 75 % methylene chloride and 25 % cyclohexane to the jarcontaining the sample (toluene has also been successfully used as an extraction solvent using this technique). Tightly seal the jarcontaining the sample an
47、d solvent mixture.10.3.4.2 Suspend the jar containing the sample and solvent in an ultrasonic water bath. Turn on the ultrasonic bath for 2 hours.The water temperature in the ultrasonic bath usually reaches about 50C during this extraction procedure.NOTE 7Solvents expand when heated. Use caution dur
48、ing this procedure. Make certain the glass jar is free from chips, cracks, and other structuraldeformities. The ultrasonic extraction conditions above are not applicable for the extraction of Tetrakis methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane.NOTE 8Allow the glass jar used in the ul
49、trasonic extraction to cool prior to transferring the extract into vials for analysis. Allowing the jar to coolfor 20 to 30 minutes will minimize the possibility of a potential chemical flash or “burp” when the jar is opened.10.3.4.3 Analyze the extract using an appropriate chromatographic technique.11. Precision and Bias11.1 These procedures are for sample preparation and as such they depend on a determinative method to produce a result.12. Keywords12.1 accelerated solvent extract
