EN 13999-4:2007+A1:2009

Adhesives - Short term method for measuring the emission properties of low-solvent or solvent-free adhesives after application - Part 4: Determination of volatile diisocyanates

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.

Klebstoffe - Kurzzeit-Verfahren zum Messen der Emissionseigenschaften von lösemittelarmen oder lösemittelfreien Klebstoffen nach der Applikation - Teil 4: Bestimmung flüchtiger Diisocyanate

Diese Europäische Norm legt ein Verfahren zur Bestimmung flüchtiger organischer Isocyanate in der Abluft
einer Emissionsprüfkammer nach der Applikation eines lösemittelarmen oder lösemittelfreien Klebstoffes nach
EN 923 fest.
Das Verfahren beruht auf der Chemisorption von flüchtigen Isocyanaten durch mit 1-(2-Methoxyphenyl)-
Piperazin (im Folgenden: 1-2MP) imprägnierte Filter mit anschließender Desorption und flüssigkeitschromatographischer
Analyse. Das Verfahren erlaubt die Messung eines breiten Spektrums organischer Verbindungen,
die als funktionelle Gruppe eine Isocyanat-Gruppe (NCO) enthalten, einschließlich von Isocyanat-Monomeren.
Bei der Prüfung der Emission von Klebstoffen sind hauptsächlich Toluendiisocyanat (TDI) und 4,4'-Methylendi-(
phenylisocyanat, auch bekannt als Diphenylmethan-4,4'-diisocyanat oder MDI) von Interesse. Das in
dieser Europäischen Norm beschriebene Verfahren kann auch auf andere Isocyanate angewendet werden,
wie z. B. Isophorondiisocyanat (IPDI) und 1,6-Hexamethylendiisocyanat (HDI) — siehe ISO 16702.
Isocyanat-Oligomere oder Prepolymere sind für den Nachweis in Emissionsprüfkammern bei Raumtemperatur
nicht flüchtig genug.

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

La présente Norme européenne spécifie un mode opératoire permettant de déterminer la présence d’isocyanates
dans l’air d’évacuation d’une chambre d’essai d’émission après application d’un adhésif à faible teneur en solvants
ou à teneur nulle en solvants tel que défini dans l’EN 923.
La méthode repose sur la chimisorption des isocyanates volatils avec filtres imprégnés de (méthoxy-1 phényle)-2
pipérazine (1-2MP) avec désorption et analyse chromatographique en phase liquide subséquents. Elle permet de
mesurer de nombreux composés organiques contenant des groupes fonctionnels d’isocyanates (NCO), notamment
les monomères isocyanate. Dans le cadre des essais d’émissions des adhésifs, sont principalement concernés
le diisocyanate de toluène (TDI) et le méthylène bis (4-phényl isocyanate, existant également sous le nom
de 4,4-diisocyanate de diphénylméthane ou MDI). La méthode décrite dans la présente Norme européenne peut
également être utilisée pour d’autres isocyanates, comme le diisocyanate d’isophorone (IPDI) et le 1,6- diisocyanate
d’hexaméthylène (HDI) — voir l’ISO 16702. Les oligomères ou prépolymères d’isocyanate ne sont pas suffisamment
volatils pour être détectés dans les chambres d’essai d’émission à température ambiante.

Lepila - Hitra metoda za merjenje emisijskih lastnosti lepil z malo topila ali brez njega po uporabi - 4. del: Določevanje hlapnih diizocianatov

General Information

• Status: Published
• Publication Date: 28-Apr-2009
• Withdrawal Date: 30-Oct-2009
• ICS: 83.180 - Adhesives
• Technical Committee: CEN/TC 193 - Adhesives
• Drafting Committee: CEN/TC 193/WG 1 - General terminology - General physical and chemical tests
• Current Stage: 9093 - Decision to confirm - Review Enquiry
• Start Date: 13-Mar-2024
• Completion Date: 14-Apr-2025
• Mandate: M/127 - Mandate to CEN/CENELEC concerning the execution of standardization work for harmonized standards on construction adhesives
• Ref Project: SIST EN 13999-4:2007+A1:2009 - Adhesives - Short term method for measuring the emission properties of low-solvent or solvent-free adhesives after application - Part 4: Determination of volatile diisocyanates

Relations

• Merged From: EN 13999-4:2007 - Adhesives - Short term method for measuring the emission properties of low-solvent or solvent-free adhesives after application - Part 4: Determination of volatile diisocyanates
• Effective Date: 18-Jan-2023

Overview

EN 13999-4:2007+A1:2009 is a European Standard developed by CEN that defines a short-term method for measuring the emission properties of low-solvent or solvent-free adhesives after application, focusing specifically on the determination of volatile diisocyanates. The standard is essential for testing emissions in the exhaust air of an emission test chamber and is relevant for adhesives containing isocyanate monomers such as toluene diisocyanate (TDI) and methylene bis(4-phenyl isocyanate) (MDI).

The method relies on chemosorption using 1-(2-methoxyphenyl) piperazine (1-2MP) impregnated filters, followed by desorption and analysis via high-performance liquid chromatography (HPLC). It offers a reliable way to measure volatile organic compounds containing isocyanate functional groups (NCO), ensuring accurate monitoring of adhesive emissions for occupational safety, indoor air quality, and regulatory compliance.

Key Topics

• Volatile Isocyanates Detection
  EN 13999-4 enables the detection and quantification of volatile diisocyanates such as TDI, MDI, isophorone diisocyanate (IPDI), and 1,6-hexamethylene diisocyanate (HDI).

• Test Chamber Sampling Procedure
  The standard specifies sampling in emission test chambers using glass fibre filters impregnated with 1-2MP to capture isocyanates from the air stream. Sampling involves controlled airflow and proper sealing to avoid contamination.

• Analytical Method: Chemosorption and HPLC
  Captured isocyanates react with 1-2MP to form non-volatile urea derivatives, which are desorbed using acetic anhydride and analyzed by liquid chromatography using ultraviolet (UV) or diode array detection (DAD).

• Calibration and Quantification
  Preparation of calibration standards includes synthetic isocyanate urea derivatives for generating calibration curves, allowing precise quantification of isocyanate concentrations in sampled air.

• Safety and Quality Control
  The standard mandates laboratory safety practices and the use of blanks and quality controls to ensure analysis accuracy and reproducibility.

Applications

• Adhesives Industry Compliance
  Manufacturers of low-solvent or solvent-free adhesives can use EN 13999-4 to identify volatile diisocyanate emissions during product development and production, ensuring compliance with environmental and health regulations.

• Indoor Air Quality Assessment
  Building materials and furnishings utilizing adhesive applications benefit from this standard when assessing potential air contamination from adhesive off-gassing.

• Workplace Exposure Monitoring
  Occupational health professionals can monitor air quality in workplaces to assess employee exposure to hazardous diisocyanates, facilitating risk management and compliance with exposure limits.

• Product Certification and Research
  Enables laboratories and research institutions to perform standardized analysis for comparative studies or certification purposes related to volatile organic compound emissions from adhesives.

Related Standards

• EN 13999-1 – General procedure for measuring emissions of low-solvent or solvent-free adhesives, providing the foundational test chamber methodology utilized in Part 4.

• ISO 16702 – Specifies the determination of total organic isocyanate groups in air using 1-(2-methoxyphenyl)piperazine and liquid chromatography, offering complementary analytical approaches for isocyanate measurement.

• EN ISO 16000-9 – Defines the emission test chamber method for measuring volatile organic compounds from building products and furnishings, which supports the sampling framework for adhesives emissions.

• EN 1232 – Details requirements and test methods for personal sampling pumps used in workplace atmosphere monitoring, ensuring accurate and reliable air collection.

Conclusion

EN 13999-4:2007+A1:2009 provides a crucial standardized method for determining volatile diisocyanate emissions from low-solvent or solvent-free adhesives. Through its detailed procedures for sample collection, preparation, and chromatographic analysis, this standard supports the adhesive industry and environmental health professionals in monitoring, controlling, and reducing potentially harmful diisocyanate emissions. Adoption of this standard contributes to safer workplaces, improved indoor air quality, and regulatory compliance across Europe and beyond.

Standards Content (Sample)

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Klebstoffe - Kurzzeit-Verfahren zum Messen der Emissionseigenschaften von lösemittelarmen oder lösemittelfreien Klebstoffen nach der Applikation - Teil 4: Bestimmung flüchtiger DiisocyanateAdhésifs - Méthodes de mesurage rapide des caractéristiques émissives des adhésifs à teneur faible ou nulle en solvants après application - Partie 4: Dosage des diisocyanates volatilsAdhesives - Short term method for measuring the emission properties of low-solvent or solvent-free adhesives after application - Part 4: Determination of volatile diisocyanates83.180LepilaAdhesivesICS:Ta slovenski standard je istoveten z:EN 13999-4:2007+A1:2009SIST EN 13999-4:2007+A1:2009en,fr,de01-junij-2009SIST EN 13999-4:2007+A1:2009SLOVENSKI
STANDARD
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

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
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