1、BRITISH STANDARDAdhesives Short term method for measuring the emission properties of low-solvent or solvent-free adhesives after application Part 4: Determination of volatile diisocyanatesICS 83.180g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g5
2、9g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58BS EN 13999-4:2007+A1:2009This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 May 2007 BSI 2009ISBN 978 0 580 63985 2National forewordBS EN 13999
3、-4:2007+A1:2009Date Comments Implementation of CEN amendment A1:2009Amendments/corrigenda issued since publicationThis British Standard is the UK implementation of EN 13999-4:2007+A1:2009. It supersedes BS EN 13999-4:2007 which is withdrawn.The start and finish of text introduced or altered by amend
4、ment is indicated in the text by tags. Tags indicating changes to CEN text carry the number of CEN amendment. For example, text altered by CEN amendment A1 is indicated by a b.The UK participation in its preparation was entrusted to Technical Committee PRI/52, Adhesives.A list of organizations repre
5、sented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.Compliance with a British Standard cannot confer immunity from legal obligations.the 30 June
6、 2009EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 13999-4:2007+A1 April 2009 ICS 83.180 Supersedes EN 13999-4:2007English Version Adhesives - Short term method for measuring the emission properties of low-solvent or solvent-free adhesives after application - Part 4: Determination of volatile
7、 diisocyanates Adhsifs - Mthodes de mesurage rapide des caractristiques missives des adhsifs teneur faible ou nulle en solvants aprs application - Partie 4: Dosage des diisocyanates volatils Klebstoffe - Kurzzeit-Verfahren zum Messen der Emissionseigenschaften von lsemittelarmen oder lsemittelfreien
8、 Klebstoffen nach der Applikation - Teil 4: Bestimmung flchtiger Diisocyanate This European Standard was approved by CEN on 8 March 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
9、for 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 Management Centre or to any CEN member. This European Standard exists in three offi
10、cial 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 Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria
11、, Belgium, Bulgaria, 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 Kingdom. EUROPEAN COMMITT
12、EE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 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+A
13、1:2009 (E) 2 Contents Page Foreword 3SAFETY STATEMENT .41 Scope 42 Normative references 43 Principle 44 Reagents and materials 55 Apparatus .56 Procedure .67 Identification and calculation .88 Interferences 99 Precision and bias .910 Test report . 1011 Quality control . 10Bibliography . 11BS EN 1399
14、9-4:2007+A1:2009 EN 13999-4:2007+A1:2009 (E) 3 Foreword This document (EN 13999-4:2007+A1:2009) has been prepared by Technical Committee CEN/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 o
15、f an identical text or by endorsement, at the latest by October 2009, and conflicting national standards shall be withdrawn at the latest by 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 intro
16、duced or altered by amendment is indicated in the text by tags ! “. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia,
17、Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. BS EN 13999-4:2007+A1:2009 EN 13999-4:2007+A1:2009 (E) 4 SAFETY STATEMENT Perso
18、ns using this European Standard should be familiar with the normal laboratory practice, if applicable. This European Standard does not purport to 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 pract
19、ices and to ensure compliance with any regulatory conditions. 1 Scope This European Standard specifies a procedure for the determination of volatile 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
20、 is based on chemosorption of volatile isocyanates with 1-(2-methoxyphenyl) piperazine (in the following: 1-2MP) impregnated filters with subsequent desorption and liquid chromatographic analysis. The method permits measurement of a wide range of organic compounds containing isocyanate functional gr
21、oups (NCO), including isocyanate monomers. For testing of adhesives emissions mainly toluene diisocyanate (TDI) and methylene bis (4-phenyl isocyanate 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 isocy
22、anates too, such as isophorone diisocyanate (IPDI) and 1,6-hexamethylene diisocyanate (HDI) - see ISO 16702. Isocyanate oligomers or prepolymers are not volatile enough to be detected in emission test chambers at room temperature. 2 Normative references The following referenced documents are indispe
23、nsable 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. EN 1232, Workplace atmospheres Pumps for personal sampling of chemical agents Requirements and
24、test methods EN 13999-1, Adhesives Short term method for measuring the emission properties of low-solvent or solvent-free adhesives after application Part 1: General procedure EN ISO 16000-9, Indoor air Part 9: Determination of the emission of volatile organic compounds from building products and fu
25、rnishing Emission test chamber method (ISO 16000-9:2006) EN ISO 16017-1, Indoor, ambient and workplace air Sampling and analysis of volatile organic compounds by sorbent tube/thermal desorption/capillary gas chromatography Part 1: Pumped sampling (ISO 16017-1:2000) EN ISO 16017-2, Indoor, ambient an
26、d workplace air Sampling and analysis of volatile organic compounds by sorbent tube/thermal desorption/capillary gas chromatography Part 2: Diffusive sampling (ISO 16017-2:2003) ISO 16702, !Workplace air quality Determination of total organic isocyanate groups in air using 1-(2-methoxyphenyl)piperaz
27、ine and liquid chromatography“ 3 Principle A sufficient volume of test chamber air is drawn with an appropriate flow through a glass fibre filter impregnated with 1-(2-methoxyphenyl)piperazine (1-2MP) reagent. Any volatile isocyanates present will react and form non-volatile isocyanate urea derivati
28、ves. Desorption is done with acetic anhydride and a 1-2MP BS EN 13999-4:2007+A1:2009 EN 13999-4:2007+A1:2009 (E) 5 solution in toluene. The resultant solution is concentrated and analysed by high performance liquid chromatography (HPLC) with ultraviolet (UV) detection. Isocyanate-derived peaks are i
29、dentified on the basis of their UV responses at more than one wavelength and/or by diode array detection (DAD) and comparison with a derivative standard. Quantification is by comparison with the relevant isocyanate monomer standard. 4 Reagents and materials 4.1 Acetonitrile Acetonitrile of HPLC grad
30、e. 4.2 1-(2-methoxyphenyl) piperazine 1-(2-methoxyphenyl) piperazine (1-2MP) of purity 98 %. 4.3 Reagent solvent The reagent solvent, commonly toluene, shall be of chromatographic quality. It shall be free from compounds coeluting with the substances of interest. Before use for the preparation of st
31、andards it is advisable to dry the solvent with anhydrous calcium chloride or magnesium sulphate. 4.4 HPLC mobile phase Dissolve 5 g of anhydrous sodium 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
32、) to give a 45 % acetonitrile / 55 % sodium acetate buffer solution. Degas this solution by filtering under vacuum or by bubbling a stream of helium 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 o
33、f 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 for filter samples. 5.1.2 Filter Commercially fabricated 1-2MP filters or prepared impregnated filters as described in ISO 16702. 5.2 Filtration equipm
34、ent 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 of the desorbed samples prior to HPLC analysis. 5.3 Sampling pump The pump shall fulfil the requirements of EN 1232 or equivalent. BS EN 13999-4:2007+A1
35、:2009 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 be 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 approp
36、riate device suitable for gas flow calibration. 5.6 High performance liquid chromatograph (HPLC) A typical apparatus for HPLC, with ultraviolet (UV) detector. 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
37、 sampling devices Clean the samplers (filter cassette) before use. Disassemble the samplers, soak in laboratory detergent solution, rinse thoroughly with water, wipe with absorptive tissue and allow to dry thoroughly before reassembling. Alternatively, use a laboratory washing machine. In an area fr
38、ee from isocyanates, load the filters into clean, dry samplers using clean flat-tipped tweezers. Connect each loaded sampling head to a sampling pump using 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 t
39、he 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 a protective cover to prevent contamination during transport to the sampling position. 6.2 Test chamber air sampling Remove the protective cover f
40、rom the sampler and assemble the sampling line. Always use two samplers in series with the downstream sampler serving as control filter. Prepare the test 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,
41、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 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 samp
42、ler from the chamber sampling port, note and record the time of disconnection, repeat the sampling flow determination and turn off the pump. Disconnect the 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/
43、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 approximately (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 contai
44、ning 2 ml 1-2MP absorbing solution and cap the vial. BS EN 13999-4:2007+A1:2009 EN 13999-4:2007+A1:2009 (E) 7 6.4 Blanks Take at least one blank sample which is an impregnated filter in samples equivalent to the ones used for sampling. Subject blank samples to the same handling procedure in the labo
45、ratory 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 perform sampling but repeat normal post-sampling activities for the filters. Mark, store and analyse blank samples in sequence with the actual
46、 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 residual grease or chemicals by soaking overnight in laboratory detergent solution and then rinsing thoroughly with water. Alternatively, use a labor
47、atory 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 solution and sampling filter and agitate well. Evaporate to dryness, redissolve the residue in 2 ml acetonitrile or mobile phase and agitate w
48、ell. Filter this solution into an autosampler vial, using a syringeless filter or 0,5 m syringe filter. Analyse using liquid chromatography as described below. 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
49、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 slowly adding methanol to dissolve the isocyanate urea derivative. Allow to cool and filter the resulting crystals, washing with cold, dry toluene. Dry the solid in air. T
