ISO 17735:2019
(Main)Workplace atmospheres — Determination of total isocyanate groups in air using 1-(9-anthracenylmethyl)piperazine (MAP) reagent and liquid chromatography
Workplace atmospheres — Determination of total isocyanate groups in air using 1-(9-anthracenylmethyl)piperazine (MAP) reagent and liquid chromatography
This document specifies a method for the sampling and analysis of airborne organic isocyanates in workplace air. This document is applicable to a wide range of organic compounds containing isocyanate groups, including monofunctional isocyanates (e.g. phenyl isocyanate), diisocyanate monomers [e.g. 1,6-hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), and isophorone diisocyanate (IPDI)], prepolymers (e.g. the biuret and isocyanurate of HDI), as well as chromatographable intermediate products formed during production or thermal breakdown of polyurethane. In mixed systems of HDI and IPDI products, it is impossible to identify and quantify low levels of IPDI monomer using this document, due to coelution of IPDI monomer with HDI-uretidinedione. It is known that the method underestimates the oligomer in MDI-based products. Total isocyanate group (NCO) is underestimated in MDI-based products by about 35 % as compared to dibutylamine titration. The method has been successfully modified to be used with LC-MS-MS for TDI monomer using an isocratic 70 % acetonitrile/30 % 10 mM ammonium formate mobile phase. The useful range of the method, expressed in moles of isocyanate group per species per sample, is approximately 1 × 10−10 to 2 × 10−7. The instrumental detection limit for the monomers using both ultraviolet (UV) detection and fluorescence (FL) detection is about 2 ng monomer per sample. The useful limit of detection for the method using reagent impregnated filters is about 10 ng to 20 ng monomer per sample for both UV and FL detection. For a 15 l sample, this corresponds to 0,7 µg/m−3 to 1,4 µg/m−3. For impinger samples, which require solid phase extraction, experience has shown that the useful limit of detection is about 30 ng to 80 ng monomer per sample.
Air des lieux de travail — Dosage des groupements isocyanates totaux dans l'air par réaction avec la 1-(9-anthracénylméthyl)pipérazine (MAP) et par chromatographie en phase liquide
Zrak na delovnem mestu - Določevanje skupin izocianatov v zraku z reagentom 1-(9-antracenilmetil)piperazin (MAP) in s tekočinsko kromatografijo
Ta dokument določa metodo za vzorčenje in analizo organskih izocianatnih spojin v
zraku na delovnem mestu.
Ta dokument se uporablja za širok nabor organskih spojin, ki vsebujejo skupine izocianatov, vključno z monofunkcijskimi izocianati (npr. fenil izocianat), monomeri diizocianata [npr.
1,6-heksametilen diizocianat (HDI), toluen diizocianat (TDI), difenilmetan-4,4’-diizocianat (MDI) in izoforon diizocianat (IPDI)], prepolimeri (npr. biuret in izocianurat HDI) ter za vmesne proizvode, ki so primerni za kromatografijo in oblikovani med proizvodnjo ali toplotno razgradnjo poliuretana.
V mešanih sistemih izdelkov HDI in IPDI je mogoče s tem dokumentom določiti in količinsko opredeliti nizke ravni monomera IPDI zaradi koelucije monomera IPDI z uretidindionom HDI. Znano je, da metoda podcenjuje oligomer v izdelkih iz MDI. Celotna skupina izocianatov (NCO) je v izdelkih iz MDI podcenjena za približno 35 % v primerjavi s titracijo
dibutilamina.
Metoda je bila uspešno prilagojena za določevanje monomera TDI z uporabo tekočinske kromatografije s tandemsko masno spektrometrijo (LC-MS-MS) pri
izokratski mobilni fazi, sestavljeni iz 70 % acetonitrila in 30 % amonijevega formata 10 mM.
Uporabno območje metode, izraženo v molih skupine izocianatov na zvrst na vzorec, je
približno 1 × 10−10 do 2 × 10−7. Meja detekcije instrumentov za monomere je pri
ultravijoličnem (UV) in fluorescentnem (FL) zaznavanju v obeh primerih približno 2 ng monomera na vzorec. Uporabna
meja zaznavanja za metodo z uporabo filtrov, prepojenih z reagenti, je približno od 10 ng do 20 ng monomera na vzorec za UV- in FL-zaznavanje. Pri 15-litrskem vzorcu to ustreza od 0,7 μg/m−3 do 1,4 μg/m−3. Pri vzorcih za kinetični vzorčevalnik, za katerega je potrebna ekstrakcija v trdni fazi, izkušnje kažejo, da je uporabna meja zaznavanja od približno 30 ng do 80 ng monomera na vzorec.
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
01-september-2019
Zrak na delovnem mestu - Določevanje skupin izocianatov v zraku z reagentom 1-
(9-antracenilmetil)piperazin (MAP) in s tekočinsko kromatografijo
Workplace atmospheres - Determination of total isocyanate groups in air using 1-(9-
anthracenylmethyl)piperazine (MAP) reagent and liquid chromatography
Air des lieux de travail - Dosage des groupements isocyanates totaux dans l'air par
réaction avec la 1-(9-anthracénylméthyl)pipérazine (MAP) et par chromatographie en
phase liquide
Ta slovenski standard je istoveten z: ISO 17735:2019
ICS:
13.040.30 Kakovost zraka na delovnem Workplace atmospheres
mestu
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
INTERNATIONAL ISO
STANDARD 17735
Second edition
2019-04
Workplace atmospheres —
Determination of total
isocyanate groups in air using
1-(9-anthracenylmethyl)piperazine
(MAP) reagent and liquid
chromatography
Air des lieux de travail — Dosage des groupements isocyanates totaux
dans l'air par réaction avec la 1-(9-anthracénylméthyl)pipérazine
(MAP) et par chromatographie en phase liquide
Reference number
©
ISO 2019
© ISO 2019
All rights reserved. Unless otherwise specified, or required in the context of its implementation, no part of this publication may
be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting
on the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address
below or ISO’s member body in the country of the requester.
ISO copyright office
CP 401 • Ch. de Blandonnet 8
CH-1214 Vernier, Geneva
Phone: +41 22 749 01 11
Fax: +41 22 749 09 47
Email: copyright@iso.org
Website: www.iso.org
Published in Switzerland
ii © ISO 2019 – All rights reserved
Contents Page
Foreword .v
Introduction .vi
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Principle . 2
5 Reagents and materials . 3
5.1 General . 3
5.2 MAP reagent . 4
5.3 Reagent solutions . 5
5.3.1 Impinger solution . . 5
5.3.2 Solution for filter impregnation . 6
5.3.3 Filter extraction solution . 6
5.3.4 Stability of reagent solutions . 6
5.4 Standard matching solutions . 6
5.4.1 General. 6
5.4.2 Preparation of monomer derivatives . 7
5.4.3 Preparation of standard solutions of monomer derivatives for HPLC analysis . 7
5.4.4 Preparation of monomer derivatives for solid-phase extraction (SPE) . 7
5.4.5 Preparation of derivative solutions of bulk isocyanate products . 8
5.5 HPLC mobile phase. 8
5.5.1 General. 8
5.5.2 Mobile phase buffer solutions . 8
5.5.3 Primary mobile phases . . 8
5.5.4 Post-column acid mobile phase . 9
6 Apparatus . 9
6.1 General . 9
6.2 Sampler . 9
6.2.1 General. 9
6.2.2 Filters . 9
6.2.3 Midget impingers . 9
6.3 Sampling pump .10
6.4 Tubing .10
6.5 Flowmeter .10
6.6 Filtration and solid-phase extraction equipment .10
6.7 Liquid chromatographic system .10
6.7.1 Autosampler .10
6.7.2 Pumping system .10
6.7.3 Analytical column .10
6.7.4 Column oven .11
6.7.5 Post-column acid delivery pump .11
6.7.6 Detectors .11
7 Air sampling .11
7.1 Pre-sampling laboratory preparation .11
7.1.1 Cleaning of sampling equipment .11
7.1.2 Preparation of MAP-coated filter samplers .11
7.1.3 Preparation of extraction solution jars.11
7.2 Pre-sampling field preparation .11
7.2.1 Calibration of pump .11
7.2.2 Preparation of samplers .12
7.3 Collection of air samples .12
7.3.1 Filter sampling .12
7.3.2 Impinger sampling .12
7.3.3 Sampling with an impinger followed by a filter .12
7.4 Blanks and negative controls .12
7.5 Bulk products .13
7.6 Shipment of samples .13
7.7 Filter test samples .13
7.8 Impinger test samples .13
8 HPLC analysis .14
8.1 Instrumental settings .14
8.2 HPLC programme.14
9 Data handling .15
9.1 Monomer measurement .15
9.2 Oligomer measurement (total detectable isocyanate) .16
10 Calibration and quality control .16
10.1 Standard matching solutions .16
10.2 Calibration curves .
...
INTERNATIONAL ISO
STANDARD 17735
Second edition
2019-04
Workplace atmospheres —
Determination of total
isocyanate groups in air using
1-(9-anthracenylmethyl)piperazine
(MAP) reagent and liquid
chromatography
Air des lieux de travail — Dosage des groupements isocyanates totaux
dans l'air par réaction avec la 1-(9-anthracénylméthyl)pipérazine
(MAP) et par chromatographie en phase liquide
Reference number
©
ISO 2019
© ISO 2019
All rights reserved. Unless otherwise specified, or required in the context of its implementation, no part of this publication may
be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting
on the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address
below or ISO’s member body in the country of the requester.
ISO copyright office
CP 401 • Ch. de Blandonnet 8
CH-1214 Vernier, Geneva
Phone: +41 22 749 01 11
Fax: +41 22 749 09 47
Email: copyright@iso.org
Website: www.iso.org
Published in Switzerland
ii © ISO 2019 – All rights reserved
Contents Page
Foreword .v
Introduction .vi
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Principle . 2
5 Reagents and materials . 3
5.1 General . 3
5.2 MAP reagent . 4
5.3 Reagent solutions . 5
5.3.1 Impinger solution . . 5
5.3.2 Solution for filter impregnation . 6
5.3.3 Filter extraction solution . 6
5.3.4 Stability of reagent solutions . 6
5.4 Standard matching solutions . 6
5.4.1 General. 6
5.4.2 Preparation of monomer derivatives . 7
5.4.3 Preparation of standard solutions of monomer derivatives for HPLC analysis . 7
5.4.4 Preparation of monomer derivatives for solid-phase extraction (SPE) . 7
5.4.5 Preparation of derivative solutions of bulk isocyanate products . 8
5.5 HPLC mobile phase. 8
5.5.1 General. 8
5.5.2 Mobile phase buffer solutions . 8
5.5.3 Primary mobile phases . . 8
5.5.4 Post-column acid mobile phase . 9
6 Apparatus . 9
6.1 General . 9
6.2 Sampler . 9
6.2.1 General. 9
6.2.2 Filters . 9
6.2.3 Midget impingers . 9
6.3 Sampling pump .10
6.4 Tubing .10
6.5 Flowmeter .10
6.6 Filtration and solid-phase extraction equipment .10
6.7 Liquid chromatographic system .10
6.7.1 Autosampler .10
6.7.2 Pumping system .10
6.7.3 Analytical column .10
6.7.4 Column oven .11
6.7.5 Post-column acid delivery pump .11
6.7.6 Detectors .11
7 Air sampling .11
7.1 Pre-sampling laboratory preparation .11
7.1.1 Cleaning of sampling equipment .11
7.1.2 Preparation of MAP-coated filter samplers .11
7.1.3 Preparation of extraction solution jars.11
7.2 Pre-sampling field preparation .11
7.2.1 Calibration of pump .11
7.2.2 Preparation of samplers .12
7.3 Collection of air samples .12
7.3.1 Filter sampling .12
7.3.2 Impinger sampling .12
7.3.3 Sampling with an impinger followed by a filter .12
7.4 Blanks and negative controls .12
7.5 Bulk products .13
7.6 Shipment of samples .13
7.7 Filter test samples .13
7.8 Impinger test samples .13
8 HPLC analysis .14
8.1 Instrumental settings .14
8.2 HPLC programme.14
9 Data handling .15
9.1 Monomer measurement .15
9.2 Oligomer measurement (total detectable isocyanate) .16
10 Calibration and quality control .16
10.1 Standard matching solutions .16
10.2 Calibration curves .16
10.3 Blank tests .17
10.4 Bulk products .17
10.5 Quality control spikes .17
11 Calculations.17
11.1 Monomer .
...
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