ASTM D2074-2007(2013) Standard Test Methods for Total Primary Secondary and Tertiary Amine Values of Fatty Amines by Alternative Indicator Method《用交替指示剂法测定脂肪胺中总胺、伯胺、仲胺和叔胺的标准试验方法》.pdf

1、Designation: D2074 07 (Reapproved 2013)Standard Test Methods forTotal, Primary, Secondary, and Tertiary Amine Values ofFatty Amines by Alternative Indicator Method1This standard is issued under the fixed designation D2074; the number immediately following the designation indicates the year oforigina

2、l 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.These test methods were prepared jointly by ASTM and the American Oil Chemists

3、 Society.1. Scope1.1 These alternative test methods cover the indicator pro-cedure for determining the total, primary, secondary, andtertiary amine values of fatty amines. These procedures are notapplicable to fatty amidoamines and fatty diamines.1.2 The values stated in SI units are to be regarded

4、asstandard. No other units of measurement are included in thisstandard.1.3 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 th

5、e applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent Water3. Terminology3.1 Definitions:3.1.1 primary amine value, nthe number of milligrams ofpotassium hydroxide (KOH) equivalent to the primary aminebasicity in1gofsample.

6、3.1.2 secondary amine value, nthe number of milligramsof potassium hydroxide (KOH) equivalent to the secondaryamine basicity in1gofsample.3.1.3 tertiary amine value, nthe number of milligrams ofpotassium hydroxide (KOH) equivalent to the tertiary aminebasicity in1gofsample.3.1.4 total amine value, n

7、the number of milligrams ofpotassium hydroxide (KOH) equivalent to the basicity in1gofsample.4. Apparatus4.1 Erlenmeyer Flasks, wide-mouth, alkali-resistant,borosilicate-glass, 250-mL capacity.4.2 Magnetic Stirrer, with an inert plastic-coated stirringbar.5. Reagents5.1 Purity of ReagentsReagent gra

8、de chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.3Other grades may beused, provided it is first asc

9、ertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.5.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Type II of Specification D1193.5.3 Bromphenol Blue Ind

10、icator SolutionDissolve 0.2 g ofbromphenol blue in 100 mL of methanol, ethanol, or isopro-panol.5.4 Bromcresol Green Indicator SolutionDissolve 0.1 g ofbromcresol green sodium salt in 100 mL of water.5.5 Chloroform (CHCl3).5.6 Hydrochloric Acid, Standard Solution (0.1 N)Add 17mL of concentrated hydr

11、ochloric acid (HCl, sp gr 1.19) to 1000mL of isopropyl alcohol in a 2-L volumetric flask. Make up tovolume after cooling to room temperature. Standardize withsodium carbonate using bromcresol green as the indicator.1These test methods are under the jurisdiction of ASTM Committee D01 onPaint and Rela

12、ted Coatings, Materials, and Applications and are the directresponsibility of Subcommittee D01.33 on Polymers and Resins.Current edition approved June 1, 2013. Published June 2013. Originallyapproved in 1962. Last previous edition approved in 2007 as D2074 07. DOI:10.1520/D2074-07R13.2For referenced

13、 ASTM standards, visit the 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.3Reagent Chemicals, American Chemical Society Specifications , AmericanChemi

14、cal 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), Rockv

15、ille,MD.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States15.7 Hydrochloric Acid, Standard Solution (0.2 N)Add 34mL of concentrated HCl (sp gr 1.19) to 1000 mL of isopropylalcohol in a 2-L volumetric flask. Make up to volume aftercooling

16、 to room temperature. Standardize with sodium carbon-ate using bromcresol green as the indicator.5.8 Isopropyl Alcohol (99 %).5.9 Phenyl Isothiocyanate.5.10 Salicylaldehyde.6. Procedure for Total Amine Value6.1 Melt the sample, if it is not already liquid, in a waterbath. Mix thoroughly, and accurat

17、ely weigh 1 to4gto0.1mginto a 250 mL flask. Add 50 mL of alcohol and boil for 1 minto drive off any free ammonia that may be present. Cool toroom temperature.6.2 Add 5 drops of bromphenol blue indicator and titrate,while swirling, with 0.2 N HCl to the yellow end point.7. Procedure for Primary, Seco

18、ndary, and TertiaryAmine Values7.1 Determine the specimen size as follows:Amine ValueSpecimenWeight, g10 or less 5Over 10 27.2 Melt the sample if it is not already liquid. Mix thor-oughly and accurately weigh the designated specimen size intotwo 150-mL beakers or 250-mL flasks. Mark them S and T.Add

19、 50 mL of CHCl3to each flask (or beaker) and boil for 1min on a hot plate to drive off any free ammonia. Cool to roomtemperature.7.3 To beaker S add 3 mL of salicylaldehyde and allow tostand for 30 min. Add 1 mL of bromphenol blue indicatorsolution and titrate while swirling (or by using the magneti

20、cstirrer if beakers are used) with 0.2 N HCl to a yellow end point(Note 1). The yellow may fade back to green upon standing,but this is to be disregarded if the yellow color is bright and theaddition of another millilitre of 0.2 N HCl does not change theyellow color.NOTE 1In the case of titrating th

21、e tertiary amine content of a primaryamine, it is advisable to use a microburet as the titration will be extremelysmall. Errors in titration are greatly magnified because of the highmolecular weights involved.7.4 To flask T add 5 mL of phenyl isothiocyanate and allowto stand for 30 min. Add 1 mL of

22、bromphenol blue indicatorsolution and titrate while swirling (or by using the magneticstirrer if beakers are used) with 0.2 N HCl to the yellow endpoint (Note 1 and Note 2). The yellow may fade back to greenupon standing, but this may be disregarded if the yellow coloris bright and the addition of a

23、nother millilitre of 0.2 N HCldoes not change the yellow color.NOTE 2Instead of 0.2 N HCl, 0.1 N HCl may be used if the quantityof tertiary amine is very low.8. Calculation8.1 Calculate the total amine value as follows:Total amine value 5 V 3 N 356.1!/S (1)where:V = HCl required for titration of the

24、 specimen (7.2), mL,N = normality of the HCl solution, andS = specimen weight used, g.8.2 Calculate the amine value of secondary and tertiaryamine groups as follows:Titration S amine value of secondary and (2)tertiary amine groups 5 V 3 N 356.1!/Swhere:V = HCl required for titration of the specimen

25、(7.3), mL,N = normality of the HCl solution, andS = specimen weight used, g.8.3 Calculate the amine value of tertiary amine groups asfollows:Titration T amine value of tertiary (3)amine groups 5 V 3 N 356.1!/Swhere:V = HCl required for titration of the specimen (7.4), mL,N = normality of the HCl sol

26、ution, andS = specimen weight used, g.8.4 Primary amine value equals total amine value minus theamine value of the secondary and tertiary amine groups.8.5 Secondary amine value equals amine value of thesecondary and tertiary amine groups minus the amine value oftertiary amine groups.8.6 Tertiary ami

27、ne value equals amine value of the tertiaryamine groups.9. Precision and Bias9.1 Precision and bias were not established at the time thistest method was written. An effort is being made to obtain theprecision and, if obtainable, it will be published in futurerevisions. This test method has been in u

28、se for many years, andits usefulness has been well established.10. Keywords10.1 amine values; fatty amines; total amine valuesD2074 07 (2013)2ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of thi

29、s 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 yea

30、rs 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 International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical commit

31、tee, 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 shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 1942

32、8-2959,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). Permission rights to photocopy the standard may also be secured from the ASTM website (www.astm.org/COPYRIGHT/).D2074 07 (2013)3