1、August 2009DEUTSCHE NORM English price group 9No part of this standard 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 83.180!$YAE“1543034www.d
2、in.deDDIN EN 13999-4Adhesives Short term method for measuring the emission properties of low-solventor solvent-free adhesives after application Part 4: Determination of volatile diisocyanates (includes AmendmentA1:2009)English version of DIN EN 13999-4:2009-08Klebstoffe Kurzzeit-Verfahren zum Messen
3、 der Emissionseigenschaften von lsemittelarmen oderlsemittelfreien Klebstoffen nach der Applikation Teil 4: Bestimmung flchtiger Diisocyanate (enthlt nderung A1:2009)Englische Fassung DIN EN 13999-4:2009-08SupersedesDIN EN 13999-4:2007-07www.beuth.deDocument comprises 13 pagesDIN EN 13999-4:2009-08
4、National foreword This standard has been prepared by Technical Committee CEN/TC 193 “Adhesives” (Secretariat: AENOR, Spain). The responsible German bodies involved in its preparation were the Normenausschuss Kunststoffe (Plastics Standards Committee), Technical Committee NA 054-04-06 AA Klebstoffe T
5、erminologie; physikalisch-chemische Prfungen and the Normenausschuss Materialprfung (Materials Testing Standards Committee). Amendments This standard differs from DIN EN 13999-4:2007-07 as follows: a) European Standard EN 13999-4:2007+A1:2009 has been adopted in full. b) In subclause 6.2, it has bee
6、n specified that the combined sampling flow rates shall not exceed 90 % of the test chamber supply air flow rate. Previous editions DIN V ENV 13999-4: 2003-02 DIN EN 13999-4: 2007-07 2 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13999-4:2007+A1 April 2009 ICS 83.180 Supersedes EN 13999-4:20
7、07English Version Adhesives Short term method for measuring the emission properties of low-solvent or solvent-free adhesives after application Part 4: Determination of volatile diisocyanates Adhsifs Mthodes de mesurage rapide des caractristiques missives des adhsifs teneur faible ou nulle en solvant
8、s aprs application Partie 4: Dosage des diisocyanates volatils Klebstoffe Kurzzeit-Verfahren zum Messen der Emissionseigenschaften von lsemittelarmen oder lsemittelfreien Klebstoffen nach der Applikation Teil 4: Bestimmung flchtiger Diisocyanate This European Standard was approved by CEN on 8 March
9、2007 and includes Amendment 1 approved by CEN on 3 April 2009. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical refe
10、rences concerning such national standards may be obtained on application to the CEN Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member
11、 into its own language and notified to the CEN Management Centre has the same status as theofficial versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latv
12、ia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussel
13、s 2009 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 13999-4:2007+A1:2009: EEN 13999-4:2007+A1:2009 (E) 2 Contents PageForeword 3SAFETY STATEMENT .41 Scope 42 Normative references 43 Principle 44 Reagents and materials 55 Apparat
14、us .56 Procedure .67 Identification and calculation .88 Interferences 99 Precision and bias .910 Test report . 1011 Quality control . 10Bibliography . 11DIN EN 13999-4:2009-08 EN 13999-4:2007+A1:2009 (E) 3 Foreword This document (EN 13999-4:2007+A1:2009) has been prepared by Technical Committee CEN/
15、TC 193 “Adhesives”, the secretariat of which is held by AENOR. 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 2009, and conflicting national standards shall be withdrawn at the latest by
16、October 2009. This document includes Amendment 1, approved by CEN on 2009-04-03. This document supersedes !EN 13999-4:2007“. The start and finish of text introduced or altered by amendment is indicated in the text by tags ! “. According to the CEN/CENELEC Internal Regulations, the national standards
17、 organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portug
18、al, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. DIN EN 13999-4:2009-08 EN 13999-4:2007+A1:2009 (E) 4 SAFETY STATEMENT Persons using this European Standard should be familiar with the normal laboratory practice, if applicable. This European Standard does not purport to
19、 address all of the safety problems, if any, associated with its use. It is the responsibility of the user to establish appropriate health and safety practices and to ensure compliance with any regulatory conditions. 1 Scope This European Standard specifies a procedure for the determination of volat
20、ile isocyanates in the exhaust air of an emission test chamber after application of a low-solvent or solvent-free adhesive as defined in EN 923. The method is based on chemosorption of volatile isocyanates with 1-(2-methoxyphenyl) piperazine (in the following: 1-2MP) impregnated filters with subsequ
21、ent desorption and liquid chromatographic analysis. The method permits measurement of a wide range of organic compounds containing isocyanate functional groups (NCO), including isocyanate monomers. For testing of adhesives emissions mainly toluene diisocyanate (TDI) and methylene bis (4-phenyl isocy
22、anate also known as 4,4-diisocyanato-diphenylmethane or MDI), are of concern. The method as described in this European Standard can be used for other isocyanates too, such as isophorone diisocyanate (IPDI) and 1,6-hexamethylene diisocyanate (HDI) - see ISO 16702. Isocyanate oligomers or prepolymers
23、are not volatile enough to be detected in emission test chambers at room temperature. 2 Normative references 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
24、the referenced document (including any amendments) applies. EN 1232, Workplace atmospheres Pumps for personal sampling of chemical agents Requirements and test methods EN 13999-1, Adhesives Short term method for measuring the emission properties of low-solvent or solvent-free adhesives after applica
25、tion Part 1: General procedure EN ISO 16000-9, Indoor air Part 9: Determination of the emission of volatile organic compounds from building products and furnishing Emission test chamber method (ISO 16000-9:2006) EN ISO 16017-1, Indoor, ambient and workplace air Sampling and analysis of volatile orga
26、nic compounds by sorbent tube/thermal desorption/capillary gas chromatography Part 1: Pumped sampling (ISO 16017-1:2000) EN ISO 16017-2, Indoor, ambient and workplace air Sampling and analysis of volatile organic compounds by sorbent tube/thermal desorption/capillary gas chromatography Part 2: Diffu
27、sive sampling (ISO 16017-2:2003) ISO 16702, !Workplace air quality Determination of total organic isocyanate groups in air using 1-(2-methoxyphenyl)piperazine and liquid chromatography“ 3 Principle A sufficient volume of test chamber air is drawn with an appropriate flow through a glass fibre filter
28、 impregnated with 1-(2-methoxyphenyl)piperazine (1-2MP) reagent. Any volatile isocyanates present will react and form non-volatile isocyanate urea derivatives. Desorption is done with acetic anhydride and a 1-2MP DIN EN 13999-4:2009-08 EN 13999-4:2007+A1:2009 (E) 5 solution in toluene. The resultant
29、 solution is concentrated and analysed by high performance liquid chromatography (HPLC) with ultraviolet (UV) detection. Isocyanate-derived peaks are identified on the basis of their UV responses at more than one wavelength and/or by diode array detection (DAD) and comparison with a derivative stand
30、ard. Quantification is by comparison with the relevant isocyanate monomer standard. 4 Reagents and materials 4.1 Acetonitrile Acetonitrile of HPLC grade. 4.2 1-(2-methoxyphenyl) piperazine 1-(2-methoxyphenyl) piperazine (1-2MP) of purity 98 %. 4.3 Reagent solvent The reagent solvent, commonly toluen
31、e, shall be of chromatographic quality. It shall be free from compounds coeluting with the substances of interest. Before use for the preparation of standards it is advisable to dry the solvent with anhydrous calcium chloride or magnesium sulphate. 4.4 HPLC mobile phase Dissolve 5 g of anhydrous sod
32、ium acetate in 1 l distilled water. Adjust the pH of this solution to 6,0 with glacial acetic acid. Add 550 ml of this solution to acetonitrile (450 ml) to give a 45 % acetonitrile / 55 % sodium acetate buffer solution. Degas this solution by filtering under vacuum or by bubbling a stream of helium
33、through it. All the reagents shall be of analytical grade. 5 Apparatus 5.1 Sampler 5.1.1 Filter holder Use an appropriate filter holder. NOTE Details of suitable sampling heads are given in MDHS14/2 2. A 25 mm head fitted with a stainless steel cassette as described in this reference is recommended
34、for filter samples. 5.1.2 Filter Commercially fabricated 1-2MP filters or prepared impregnated filters as described in ISO 16702. 5.2 Filtration equipment A solvent resistant filter unit of 0,5 m pore size for filtration of HPLC solvents. Syringeless filters or 0,5 m syringe filters for filtration o
35、f the desorbed samples prior to HPLC analysis. 5.3 Sampling pump The pump shall fulfil the requirements of EN 1232 or equivalent. DIN EN 13999-4:2009-08 EN 13999-4:2007+A1:2009 (E) 6 5.4 Tubing Tubing of appropriate diameter to ensure a leak-proof fit to both pump and sample tube. PTFE tubes shall b
36、e used upstream of the sorbent to avoid loss of substance due to reaction with tubing walls. 5.5 Flow meter calibrator Bubble meter or other appropriate device suitable for gas flow calibration. 5.6 High performance liquid chromatograph (HPLC) A typical apparatus for HPLC, with ultraviolet (UV) dete
37、ctor. 5.7 Emission test chamber An emission test chamber as described in EN 13999-1 or EN ISO 16000-9 shall be used. 6 Procedure 6.1 Preparation of sampling devices Clean the samplers (filter cassette) before use. Disassemble the samplers, soak in laboratory detergent solution, rinse thoroughly with
38、 water, wipe with absorptive tissue and allow to dry thoroughly before reassembling. Alternatively, use a laboratory washing machine. In an area free from isocyanates, load the filters into clean, dry samplers using clean flat-tipped tweezers. Connect each loaded sampling head to a sampling pump usi
39、ng plastic tubing ensuring that no leaks can occur. Switch on the pump, attach the calibrated flow meter to the sampling head so that it measures the flow through the sampler inlet orifice, and set the appropriate flow rate with a limit deviation of 5 %. Switch off the pump and seal the sampler with
40、 a protective cover to prevent contamination during transport to the sampling position. 6.2 Test chamber air sampling Remove the protective cover from the sampler and assemble the sampling line. Always use two samplers in series with the downstream sampler serving as control filter. Prepare the test
41、 chamber sampling port as described in EN 13999-1 or in EN ISO 16000-9. If the sampling flow rate is determined with a calibrator, start the pump, note and record the sampling flow rate. Connect the sampler to the chamber sampling port, note and record the time the sampler was connected. !Never use
42、more than 90 % of the test chamber supply air flow“ rate as the combined sampling flow rates. At the end of the sampling period disconnect the sampler from the chamber sampling port, note and record the time of disconnection, repeat the sampling flow determination and turn off the pump. Disconnect t
43、he sampler or the samplers from the sampling line and seal both ends using inert caps. NOTE When applying a sampling flow rate in the range of 2 l/min and a sampling air volume of 240 l then the method is suitable for the measurement of airborne organic isocyanates in the concentration range of appr
44、oximately (0,01 to 10) g isocyanate per m. 6.3 Storage of loaded sampling filters Remove each filter from the sampler, place in a glass vial containing 2 ml 1-2MP absorbing solution and cap the vial. DIN EN 13999-4:2009-08 EN 13999-4:2007+A1:2009 (E) 7 6.4 Blanks Take at least one blank sample which
45、 is an impregnated filter in samples equivalent to the ones used for sampling. Subject blank samples to the same handling procedure in the laboratory as the actual samples except for the actual period of sampling, i.e. repeat the sampling procedure up to the point of actual sample collection. Do not
46、 perform sampling but repeat normal post-sampling activities for the filters. Mark, store and analyse blank samples in sequence with the actual samples. For blank control of the test chamber see EN 13999-1. 6.5 Analysis 6.5.1 Cleaning of glassware Before use, clean all glassware to remove any residu
47、al grease or chemicals by soaking overnight in laboratory detergent solution and then rinsing thoroughly with water. Alternatively, use a laboratory washing machine. 6.5.2 Sample desorption and pre-reaction before HPLC analysis Pipette 100 l acetic anhydride into each glass vial containing the 1-2MP
48、 solution and sampling filter and agitate well. Evaporate to dryness, redissolve the residue in 2 ml acetonitrile or mobile phase and agitate well. Filter this solution into an autosampler vial, using a syringeless filter or 0,5 m syringe filter. Analyse using liquid chromatography as described belo
49、w. 6.5.3 Preparation of calibration standards 6.5.3.1 Preparation of isocyanate urea derivatives Add the appropriate isocyanate 0,1 g to 0,6 g of 1-2MP dissolved in dry toluene (10 ml) and leave to stand for one hour. A white crystalline isocyanate urea derivative will be precipitated. Collect this on a filter and wash several times with dry toluene to remove excess reagent. Recrystallise the isocyanate urea derivative from toluene by warming to about 60 C and slowl
