|
STANDARD
SIST EN 13999-4:2007+A1:2009
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE 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 diisocyanates
Adhésifs - Méthodes de mesurage rapide des caractéristiques émissives des adhésifs à teneur faible ou nulle en solvants après application - Partie 4: Dosage des diisocyanates volatils
Klebstoffe - Kurzzeit-Verfahren zum Messen der Emissionseigenschaften von lösemittelarmen oder lösemittelfreien Klebstoffen nach der Applikation - Teil 4: Bestimmung flüchtiger 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 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 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 Management Centre has the same status as the official 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, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR 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: ESIST EN 13999-4:2007+A1:2009
EN 13999-4:2007+A1:2009 (E) 2 Contents Page Foreword .3SAFETY STATEMENT .41Scope .42Normative references .43Principle .44Reagents and materials .55Apparatus .56Procedure .67Identification and calculation .88Interferences .99Precision and bias .910Test report . 1011Quality control . 10Bibliography . 11 SIST EN 13999-4:2007+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 of 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 introduced 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, 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. SIST EN 13999-4:2007+A1:2009
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 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 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 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 groups (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 isocyanates 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 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. 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 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 furnishing — 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 and 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)piperazine 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 derivatives. Desorption is done with acetic anhydride and a 1-2MP SIST 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 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 standard. 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 toluene, 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 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) 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 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 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 µm pore size for filtration of HPLC solvents. Syringeless filters or
< 0,5 µm 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. SIST EN 13999-4:2007+A1:2009
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 appropriate 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 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 free 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 the flow through the sampler inlet orifice, an
...