1、Designation: D5017 96 (Reapproved 2009)1D5017 17Standard Test Method forDetermination of Linear Low Density Polyethylene (LLDPE)Composition by Carbon-13 Nuclear Magnetic Resonance1This standard is issued under the fixed designation D5017; the number immediately following the designation indicates th
2、e 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 () indicates an editorial change since the last revision or reapproval.1 NOTEReapproved with editorial changes in April 2009.1. Scope
3、 Scope*1.1 This test method determines the molar composition of copolymers prepared from ethylene (ethene) and a second alkene-1monomer. This second monomer can include propene, butene-1, hexene-1, octene-1, and 4-methylpentene-1.1.2 Calculations of this test method are valid for products containing
4、 units EEXEE, EXEXE, EXXE, EXXXE, and of courseEEE where E equals ethene and X equals alkene-1. Copolymers containing a considerable number of alkene-1 blocks (such as,longer blocks than XXX) are outside the scope of this test method.1.3 This standard does not purport to address all of the safety co
5、ncerns, if any, associated 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. See Section 8 for a specific hazard statement.NOTE 1There is no equivalent ISO kno
6、wn ISO equivalent to this standard.2. Referenced Documents2.1 ASTM Standards:2D883 Terminology Relating to PlasticsE177 Practice for Use of the Terms Precision and Bias in ASTM Test MethodsE386 Practice for Data Presentation Relating to High-Resolution Nuclear Magnetic Resonance (NMR) Spectroscopy(W
7、ithdrawn 2015)3E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test MethodE2977 Practice for Measuring and Reporting Performance of Fourier-Transform Nuclear Magnetic Resonance (FT-NMR)Spectrometers for Liquid SamplesIEEE/ASTM SI-10 Standard for Use of the Inter
8、national System of Units (SI): The Modern System43. Terminology3.1 Some units, symbols, and abbreviations used in this test method are summarized in IEEE/ASTM SI-10 and Practice E386.Other abbreviations are listed as follows:3.2 Abbreviations:3.2.1 13Ccarbon 13,3.2.2 LLDPElinear low-density polyethy
9、lene,3.2.3 T1relaxation time, and3.2.4 TRpulse repetition time.3.3 Definitions of Terms Specific to This Standard:3.3.1 With a few modifications, terms used to designate different carbon types were suggested by Carman.5 Methine carbonsare identified by CH and branch carbons are labeled according to
10、branch type as summarized in Table 1. Branch carbons arenumbered starting with the methyl as number one.1 This test method is under the jurisdiction of ASTM Committee D20 on Plastics and is the direct responsibility of Subcommittee D20.70 on Analytical Methods.Current edition approved April 1, 2009M
11、arch 1, 2017. Published June 2009March 2017. Originally approved in 1991. Last previous edition approved in 20032009 asD5017 96(2003)(2009)1. DOI: 10.1520/D5017-96R09E01.10.1520/D5017-17.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceas
12、tm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 The last approved version of this historical standard is referenced on www.astm.org.4 Available from ASTM International Headquarters, 100 Barr Harbor Drive, C700, West Cons
13、hohocken, PA 19428.5 Carman, C. J., Harrington, R. A., and Wilkes, C. E., Macromolecules 1977, Vol 10, p. 536.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
14、technically possible to adequately depict 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
15、this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.3.2 Backbone methylene carbons are designated by a pair of Greek letters that specify the location of the nearest methinecarbon in each direction. For example, ,-methylene
16、 carbon is between two methine carbons or an ,+ methylene carbon has oneimmediate methine neighbor and the second methine carbon is located at least four carbons away.4. Summary of Test Method4.1 Polymer samples are dispersed in hot solvent and analyzed at high temperatures using Carbon-13 nuclear m
17、agneticresonance (NMR) spectroscopy.4.2 Spectra are recorded under conditions such that the response of each chemically different carbon is identical. Integratedresponses for carbons originated from the different comonomers are used for calculation of the copolymer composition.5. Significance and Us
18、e5.1 Performance properties are dependent on the number and type of short chain branches. This test method permitsmeasurement of these branches for ethylene copolymers with propylene, butene-1, hexene-1, octene-1, and 4-methylpentene-1.6. Apparatus6.1 NMR Spectrometer, 13C pulse-Fourier transform sp
19、ectrometer with a field strength of at least 2.35 T.NOTE 2The system should have a computer size of at least 32 K for 50-MHz carbon frequency with digital resolution of at least 0.5 Hz/point in thefinal spectrum.6.2 Sample Tubes,610-mm outside diameter.NOTE 3Sample tube size can be varied; however,
20、the sample preparation procedure described in 10.1 may need to be altered to maintain the minimumsignal-to-noise requirement of 9.4.7. Reagents and Materials7.1 Ortho-dichlorobenzene or 1,2,4-trichlorobenzene, reagent grade7.2 Deuterated o-dichlorobenzene or p-dichlorobenzene. This material is used
21、at a concentration up to 20 % with the reagentspecified in 7.1 as an internal lock.8. Hazards8.1 WarningSolvents shouldshall be handled in a well-ventilated fume hood.9. Instrument Parameters9.1 Pulse angle, 909.2 Pulse repetition, 10 s9.3 Sample temperature, 130CNOTE 4The precise temperature should
22、 be measured using the NMR thermometer (cyclooctane/methylene iodide).79.4 Minimum signal-to-noise, 5000:1NOTE 5The signal-to-noise ratio is defined as 2.5 times the signal intensity of the 30.0-ppm peak (isolated methylenes) divided by the peak to peaknoise for the region from 50 to 70 ppm. Calcula
23、tion of signal-to-noise is permitted using an equivalent software procedure.9.5 Sweep width, 175 ppm9.6 Transmitter frequency (F1), 50 to 55 ppm9.7 Apodisation, 2 (exponential) Hz9.8 Pulse width, 4 sweep width Hz16 Available from Wilmad Scientific Glass Co.7 Vidrime, D. W., and Peterson, P. E., Anal
24、ytical Chemistry , Vol 48, 1976, p. 1301.TABLE 1 Designations for Different Carbon TypesMonomer Branch Type LabelPropene (P) methyl M1Butene-1 (B) ethyl E1E2Hexene-1 (H) butyl B1B44-Methylpentene-1 (MP) isobutyl IB1IB3Octene-1 (O) hexyl H1H6D5017 1729.9 Decoupling, completeNOTE 6The nuclear Overhaus
25、er enhancement for the carbons used for quantitative analysis have been shown to be full.4, 7, 810. Procedure10.1 Weigh a 1.2-g sample into a 10-mm NMR tube. Add 1.5 mL of solvent (7.1) and 1.3 mL deuterated solvent (7.2) to thetube. Cap the tube.NOTE 7Solution concentration can be varied with instr
26、uments of different field strength as long as one meets the minimum signal-to-noiserequirement of 9.4.10.2 Homogenize the sample in an oven at 150C for 3 to 4 h. Keep the tube in a vertical position during the heating step.10.3 Set spectrometer parameters as detailed in Section 9.10.4 Transfer the t
27、ube to the NMR spectrometer and equilibrate 10 to 15 min at 130C.10.5 Scan the sample with complete broadband decoupling using the parameters of Section 9.10.6 Record the spectrum and the accurate full-scale integral from 10 to 50 ppm. Adjust partial integrals so that integral of thesecond largest p
28、eak in the spectrum is at least 50 % of full-scale. This partial integral must be flat before and after the area to bemeasured.NOTE 8The combination of sample preparation time and acquisition time necessary to obtain the signal-to-noise requirement of 9.4 can lead toprohibitively long experiments if
29、 samples are run multiplicatively. It is acceptable to perform sample determinations using a single analysis. Duplicateruns in accordance with 13.1 were performed for the round-robin exercise.11. Calculation11.1 Measure the area between the appropriate integration limits outlined in Annex A1.11.2 Su
30、bstitute the integrals into the appropriate equations from Annex A2 to calculate the mole percent alkene-1.11.3 Annex A3 gives a sample calculation for an ethylene-octene copolymer using integrals and equations in accordance with11.1 and 11.2.NOTE 9With the prescribed repetition time (10 s) and puls
31、e angle (90), the maximum allowable relaxation time (T1 ) for carbons used for quantitativeanalysis is 2 s. To shorten the analysis time, a shorter pulse repetition time can be used if one accounts for the relaxation time differences. Relaxationtimes of carbons for the five copolymers were determine
32、d at a carbon frequency of 50 MHz using the inversion recovery method.9, 10Appendix X1summarizes these relaxation times and correction factors (reciprocal of the relative intensities) for a 4-s repetition time (TR). With the shorter TR, multiplyintegrals by these correction factors before using the
33、equations in Annex A2. The T1 values would have to be remeasured for analyses performed atspectrometer frequencies other than 50 MHz.11.4 If desired, convert results from mole percent alkene-1 to branches per 1000 carbons (br/1000C) using the equations inAnnex A4.12. Report12.1 Report the mole perce
34、nt alkene-1 from 11.2 or branches/1000C from 11.4, or both.13. Precision and Bias1113.1 Table 2 is based on a round robin conducted in 1988 in accordance with Practice E691, involving nine materials tested bysix laboratories. For each material, all the samples were prepared at one source, but the in
35、dividual specimens were prepared at thelaboratories that tested them. Each “test result” was the average of two individual determinations. Each laboratory obtained onetest result for each material. (WarningThe following explanations of r and R (13.2 13.2.3) are only intended to present ameaningful w
36、ay of considering the approximate precision of this test method. The data in Table 2 shouldare not to be rigorouslyapplied to acceptance or rejection of material, as those data are specific to the round robin and mayare not be representative of otherlots, conditions, materials, or laboratories. User
37、s of this test method should need to apply the principles outlined in Practice E691to generate data specific to their laboratory and materials, or between specific laboratories. The principles of 13.2 13.2.3 wouldthen be valid for such data.)13.2 Concept of r and RIf Sr and SR have been calculated f
38、rom a large enough body of data, and for test results that wereaverages from testing two specimens:13.2.1 RepeatabilityTwo test results obtained within one laboratory shall be judged not equivalent if they differ by more thanthe “r” value for that material; “r” is the interval representing the criti
39、cal difference between two test results for the same material,obtained by the same operator using the same equipment on the same day in the same laboratory.8 Randall, J. C., “NMR and Macromolecules,” Chapter 9, American Chemical Society Symposium Series 247, 1984 .9 Farrar, T. C., and Becker, E. D.,
40、 Pulse and Fourier Transform NMR, Chapter 2, Academic Press, New York, 1971.10 Cheng, H. N., and Bennet, M. A., Macromolecule Chemistry , Vol 188, 1987, pp. 26652677.11 Supporting data are available from ASTM Headquarters. Request RR:D20-1192.D5017 17313.2.2 Reproducibility Limit, R (Comparing Two T
41、est Results for the Same Material, Obtained by Different Operators UsingDifferent Equipment in Different Laboratories)Laboratories) The two test results should be judged not equivalent if they differby more than the “ R” value for that material.13.2.3 Any judgment in accordance with 13.2.1 or 13.2.2
42、 wouldwill have an approximate 95 % (0.95) probability of beingcorrect.13.3 There are no recognized standards by which to estimate bias of this test method.14. Keywords14.1 carbon-13 NMR; composition; LLDPE; polyethyleneANNEXES(Mandatory Information)A1. AREA BETWEEN THE APPROPRIATE INTEGRATION LIMIT
43、S OUTLINESTABLE 2 Precision Statistics for Determination of Mole PercentBranching in LLDPE Copolymers by Carbon-13 NMRSpectroscopySample Comonomer AverageMole,% Expressed as % of the AverageVrA VRB rC RDA butene 4.72 11.1 11.5 31.1 32.2B butene 4.22 11.9 11.9 33.3 33.3C hexene 3.64 17.1 18.2 47.9 51
44、.0D hexene 4.03 14.3 14.3 40.0 40.0E octene 5.18 10.3 10.3 28.8 28.8F octene 0.76 27.5 40.6 77.0 113.7G 4-methyl-pentene 5.00 14.0 14.8 39.2 41.4H 4-methyl-pentene 1.26 37.4 38.2 104.7 107.0I propene 15.96 7.3 7.6 20.4 21.3A Vr = within laboratory coefficient of variation for the indicated material.
45、 It isobtained by pooling the within laboratory standard deviations of the following testresults:Sr5ffoss1d21ss 2d2 .1ssnd2 g/ngVr51003sSr divided by the overall average for the materiald.B VR = between laboratories reproducibility, expressed as coefficient of variation,for the indicated material.C
46、r = within laboratory repeatability limit = 2.8 Vr .D R = between laboratories reproducibility limit = 2.8 VR .D5017 174A2. EQUATIONS FOR CALCULATING MOLE % COMPOSITIONA2.1 Ethene-Propene CopolymersA2.1.1 Moles Propene (see Note A2.1):P1 52carbons:2A1B!/2) (A2.1)P2 5CH carbons:2A1C2HP5average moles
47、propylene:P1 1P2!/2A2.1.2 Moles Ethene (see Note A2.2):E5C1D1E1F 2A!/2 (A2.2)Mole %propene5100%3P/P1E!A2.2 Ethene-Butene-1 CopolymersA2.2.1 Moles Butene-1 (see Note A2.1):TABLE A1.1 Integration Limits for Ethylene CopolymersACopolymer Area Region, ppmEthene-propene A 47.5 to 44.5B 39.8 to 36.8C 35.5
48、 to 32.5C + D + E 35.5 to 25.8F 25.8 to 23.8G 22.5 to 18.5H Peak at 21.6Ethene-butene-1 A 41.5 to 38.5A Peak at 39.4B 37.8 to 36.8C 36.0 to 33.2D + E 33.2 to 25.5F 25.2 to 24.0Ethene-hexene-1 A 41.5 to 40.5B 40.5 to 39.5C 39.5 to 37.0D Peak at 35.8D + E 36.8 to 33.2F + G 33.2 to 25.5G 28.5 to 26.5H
49、24.9 to 24.1Ethene-octene-1 A 41.5 to 40.5B 40.5 to 39.5C 39.5 to 37.0D Peak at 35.8D + E 36.8 to 33.2F + G + H 33.2 to 25.5H 28.5 to 26.5I 25.0 to 24.0P 24.0 to 22.0Ethene-4-methylpentene-1 A 46.5 to 43.5B 43.0 to 41.8C 41.8 to 40.5D 37.5 to 34.2E Peak at 33.7F + G 33.2 to 25.2G 28.0 to 25.2H Peak at 24.1A Isolated methylene carbons at 30.0 ppm.D5017 175B1 52carbons:2A1B!/2) (A2.3)B2 5CH carbons:A12C12B!/4B5average moles butene21:B1 1B2!/2A2.2.2 Moles ethene (see Note A2.2):E52D12E12F 2A2B!/4 (A2.4)Mole %
