1、July 2011 Translation by DIN-Sprachendienst.English price group 9No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 87
2、.060.20!$s“1805829www.din.deDDIN EN ISO 19334Binders for paints and varnishes Gum rosin Gas-chromatographic analysis (ISO 19334:2010)English translation of DIN EN ISO 19334:2011-07Bindemittel fr Beschichtungsstoffe Kolophonium Gaschromatographische Analyse (ISO 19334:2010)Englische bersetzung von DI
3、N EN ISO 19334:2011-07Liants pour peintures et vernis Colophane Analyse par chromatographie en phase gazeuse (ISO 19334:2010)Traduction anglaise de DIN EN ISO 19334:2011-07www.beuth.deDocument comprises pagesIn case of doubt, the German-language original shall be considered authoritative.1307.11 DIN
4、 EN ISO 19334:2011-07 2 A comma is used as the decimal marker. National foreword This standard has been prepared by Technical Committee ISO/TC 35 “Paints and varnishes”, Subcommittee SC 10 “Test methods for binders for paints and varnishes” (Secretariat: DIN, Germany) in collaboration with Technical
5、 Committee CEN/TC 139 “Paints and varnishes” (Secretariat: DIN, Germany). The responsible German body involved in its preparation was the Normenausschuss Beschichtungsstoffe und Beschichtungen (Coatings and Coating Materials Standards Committee), Working Committee NA 002-00-02 AA Lackrohstoffe. The
6、Naval Stores Act of 1923 (42 Stat 1435.7, USC 91-99), referred to in Clause 3 for the sampling of gum rosin, was amended in 1951 as a reference for the sampling of tall oil rosin. The abbreviation “Stat” means “statute” and “USC” means “US Congress” or “US Code”. The document is available from the L
7、ibrary of Congress. EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 19334 April 2011 ICS 87.040; 87.060.20 English Version Binders for paints and varnishes - Gum rosin - Gas-chromatographic analysis (ISO 19334:2010) Liants pour peintures et vernis - Colophane - Analyse par chromatographie e
8、n phase gazeuse (ISO 19334:2010) Bindemittel fr Beschichtungsstoffe - Kolophonium - Gaschromatographische Analyse (ISO 19334:2010) This European Standard was approved by CEN on 17 March 2011. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for
9、 giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three
10、 official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodi
11、es of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kin
12、gdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 19334:2011: EC
13、ontents EN ISO 19334:2011 (E) DIN EN ISO 19334:2011-07 2 Page Foreword3 Introduction .4 1 Scope 5 2 Normative references 5 3 Sampling.5 4 Apparatus .5 4.1 Gas chromatograph.5 4.2 Column5 5 Reagents and materials 6 6 Preparation of methyl esters 6 7 Gas-chromatographic analysis 6 7.1 Set-up of gas ch
14、romatograph (GC)6 7.2 Analysis 6 7.3 Calculation7 8 Test report 7 Bibliography 11 Foreword The text of ISO 19334:2010 has been prepared by Technical Committee ISO/TC 35 “Paints and varnishes” of the International Organization for Standardization (ISO) and has been taken over as EN ISO 19334:2011 by
15、Technical Committee CEN/TC 139 “Paints and varnishes” the secretariat of which is held by DIN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by October 2011, and conflicting national standards shal
16、l be withdrawn at the latest by October 2011. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN/CENELEC Internal Re
17、gulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg,
18、Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of ISO 19334:2010 has been approved by CEN as a EN ISO 19334:2011 without any modification. EN ISO 19334:2011 (E) DIN EN ISO 19334:2011-07 3 Intro
19、duction Gum rosins are important commercial materials, primarily composed of rosin acids, but also containing some neutral material. For many applications, it is necessary to know the level of the individual rosin acids present in these products. Gas chromatography has proven to be a useful tool for
20、 such determinations (see ASTM D 509), and capillary chromatography, specified in these test methods, is considered to be the most effective gas-chromatographic technique currently available. Due to hydrogen bonding, unmodified rosin acids cannot be volatilized at atmospheric pressure without underg
21、oing decomposition. So, it is necessary to convert the free acids to more volatile and more stable methyl esters, prior to chromatographic separation. This International Standard describes one way to prepare methyl esters. The classic method is through the use of diazomethane, but diazomethane is a
22、hazardous and toxic material, and so is no longer the preferred agent. Trimethylphenylammonium hydroxide (TMPAH) and tetramethylammonium hydroxide (TMAH) are satisfactory methylating agents as both produce results that are very similar to those of diazomethane, but without the hazards that are assoc
23、iated with diazomethane. N,N-dimethylformamide dimethyl acetal (DMF-DMA) gives results comparable to those obtained with TMPAH and TMAH and is easy and safe to use. However, the reagent is moisture-sensitive, requiring samples to be free of any significant levels of water. This International Standar
24、d specifies the method using TMAH. EN ISO 19334:2011 (E) DIN EN ISO 19334:2011-07 4 1 Scope This International Standard specifies a gas-chromatographic method for determining the amounts of certain rosin acids in gum rosin using capillary gas-chromatographic separation of the volatile methyl esters
25、of these acids. It is intended primarily to permit the identification of gum rosin from specific species of pine trees. It is not designed for the quantitative analysis of gum rosin. If such analyses are required, the internal-standard technique specified in ASTM D 5974 should be used. 2 Normative r
26、eferences The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. GB 8145, Gum rosin Test methods of rosi
27、n ASTM D 509, Standard Test Methods of Sampling and Grading Rosin Naval Stores Act of 1923 (42 Stat 1435.7, USC 91-99) as amended in 1951 3 Sampling Take a representative sample following the procedures specified in GB 8145, ASTM D 509 or the Naval Stores Act of 1923 (42 Stat 1435.7, USC 91-99) as a
28、mended in 1951. NOTE Rosin samples need to be freshly broken from a larger mass to ensure the results are not affected by air oxidation of the rosin. 4 Apparatus 4.1 Gas chromatograph Use an instrument equipped with a flame-ionization detector (FID) that can be operated under the conditions given in
29、 7.1. 4.2 Column The recommended (referee) column is a fused-silica BDS column 25 m in length, 0,32 mm in internal diameter and with a 0,20 m film thickness, which gives separation equivalent to or better than that shown in Figures 1 to 3. If other columns are used, the operating conditions shall be
30、 chosen such that the separation obtained is equivalent to or better than that shown in Figures 1 to 3. EN ISO 19334:2011 (E) DIN EN ISO 19334:2011-07 5 5 Reagents and materials Reagent-grade chemicals should preferably be used in all analyses. If other grades are used, it shall be first ascertained
31、 that the reagent concerned is of sufficiently high purity to permit its use without lessening the accuracy of the determination. 5.1 Tetramethylammonium hydroxide (TMAH) solution, 24 % in methanol, CAS No. 75-59-2 5.2 Tetramethylammonium hydroxide (TMAH) solution, 6 % in methanol. Dilute 25 ml of t
32、he reagent described in 5.1 with 75 ml of methanol. 5.3 Phenolphthalein solution, 1 % (mass per volume) in methanol 5.4 Methanol, anhydrous 5.5 Toluene (optional) 6 Preparation of methyl esters Weigh approximately 50 mg of the sample into a suitable vial, and dissolve it in 0,5 ml to 3,0 ml of metha
33、nol. Add 2 to 3 drops of phenolphthalein indicator solution, and titrate to a pink colour (pH 7,8 to 8,1) with the solution of 6 % solution. When the solution is injected into the heated injection port of the chromatograph, the tetramethylammonium salts are pyrolyzed to methyl esters. NOTE For solid
34、 rosin, 2 to 3 drops of toluene may be added to the vial prior to the addition of TMAH, to assist in dissolving the sample. 7 Gas-chromatographic analysis 7.1 Set-up of gas chromatograph (GC) Set the GC conditions so that they are approximately as follows (see also the last paragraph in this subclau
35、se): Column temperature: 195 C, isothermal Injection port temperature: 300 C Injection port liner: glass splitter Detector temperature: 280 C Carrier gas: hydrogen or helium Linear flow rate: 40 cm/s Split ratio: 40 to 1 Detector: FID hydrogen: 50 kPa air: 100 kPThese are the typical operating condi
36、tions for the instrument using the BDS column. The particular equipment used shall be adjusted in accordance with the manufacturers instructions to optimize its performance. Ongoing adjustment of operating temperature and flow rate may be necessary to maintain optimum performance of the column due t
37、o ageing. 7.2 Analysis Inject 0,5 l to 1,0 l of the test sample prepared in Clause 6. NOTE Dilution of the sample with additional solvent may be necessary to obtain injections that do not overload the column or detector. EN ISO 19334:2011 (E) DIN EN ISO 19334:2011-07 6 7.3 Calculation Sum all the ar
38、eas of the individual peaks, exclusive of the solvent peak, to obtain the total peak area. Calculate the relative percentage of each rosin acid methyl ester present, uncorrected for the amount of polymeric materials present, using the equation Tot100Rosin acid(%)AA= where A is the peak area for the
39、rosin acid methyl ester being determined; ATotis the sum of the areas of all rosin acid methyl ester peaks. NOTE See Figures 1 to 3 for typical chromatograms of selected gum rosins and Table 1 for their compositions determined from these and other such chromatograms. 8 Test report The test report sh
40、all contain at least the following information: a) all details to identify the product tested; b) reference to this International Standard (ISO 19334:2010); c) the area percent of individual rosin acids to the nearest 0,1 %; d) by comparison with Table 1 and Figures 1 to 3, the identity of the gum r
41、osin; e) any deviation from the test method specified; f) the date of the test. Table 1 Typical contents of characteristic rosin acids in gum rosins from pine species (determined by the gas-chromatographic method specified in this International Standard) Rosin acid Pinus massoniana Pinus merkusii Pi
42、nus elliottii Pinus pinaster Pinus caribaea Pinus keysia Pinus yunnanensis Relative Retention % % % % % % % Communic 0 0 5 0 1 0 0 0,588 Palustric 25 20 19 19 22 20 26 0,634 Isopimaric 2 15 17 5 8 4 6 0,664 Abietic 35 35 23 38 35 41 31 0,967 Dehydroabietic 4 5 5 6 7 4 5 1,000 Neoabietic 16 5 20 16 1
43、7 18 22 1,092 Mercusic 0 7 0 0 0 0 0 1,514 NOTE Capillary gas-liquid chromatography (GLC). Labelled peaks eluated as methyl esters. Conversion of rosin acids to their methyl deviates by means of tetramethylammonium hydroxide (TMAH) procedure. Column: fused silica BDS, l = 25 m, d = 0,32 mm, film thi
44、ckness = 0,2 m, T = 195 C (isothermal), carrier gas H2at 50 kPa. EN ISO 19334:2011 (E) DIN EN ISO 19334:2011-07 7 Key 1 palustric acid 2 isopimaric acid 3 abietic acid 4 dehydroabietic acid 5 neoabietic acid Figure 1 Chromatogram of rosin acid methyl esters from Pinus massoniana rosin EN ISO 19334:2
45、011 (E) DIN EN ISO 19334:2011-07 8 Key 1 palustric acid 2 isopimaric acid 3 abietic acid 4 dehydroabietic acid 5 neoabietic acid 6 mercusic acid Figure 2 Chromatogram of resin acid methyl esters from Pinus merkusii rosin EN ISO 19334:2011 (E) DIN EN ISO 19334:2011-07 9 Key 1 communic acid 2 palustri
46、c acid 3 isopimaric acid 4 abietic acid 5 dehydroabietic acid 6 neoabietic acid Figure 3 Chromatogram of resin acid methyl esters from Pinus elliotii rosin EN ISO 19334:2011 (E) DIN EN ISO 19334:2011-07 10 Bibliography 1 ASTM D 5974, Standard Test Methods for Fatty and Rosin Acids in Tall Oil Fractionation Products by Capillary Gas Chromatography EN ISO 19334:2011 (E) DIN EN ISO 19334:2011-07 11
