Page:NIOSH Manual of Analytical Methods - 5516.pdf/1

5516

2,4- and 2,6-TOLUENEDIAMINE
(in the presence of isocyanates)

 

CH₃C₆H₃(NH₂)₂

MW: 122.17

CAS: 2,4-: 95-80-7

CAS: 2,6-: 823-40-5

RTECS: 2,4-: XS9625000

RTECS: 2,6-: XS9750000

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METHOD: 5516, Issue 2

EVALUATION: PARTIAL

Issue 1: 15 May 1989

Issue 2: 15 August 1994

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OSHA: no PEL

NIOSH: 2,4-: lowest feasible; carcinogen

ACGIH: no TLV

PROPERTIES: 2,4-: solid; MP 99 °C

2,6-: solid; MP 106 °C

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SYNONYMS: 2,4-: 4-methyl-1,3-benzenediamine; 2,4-diaminotoluene

SYNONYMS: 2,6-: 2-methyl-1,3-benzenediamine; 2,6-diaminotoluene

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SAMPLING

MEASUREMENT

SAMPLER	IMPINGER (solution of 1-(2-methoxyphenyl)piperazine in toluene, 15 mL)
FLOW RATE	1 L/min

TECHNIQUE:	HPLC, UV DETECTION
ANALYTES:	2,4- and 2,6-bisacetamidotoluene
INJECTION VOLUME:	10 μL
MOBILE PHASE:	programmed; sodium acetate in acetonitrile/water at pH 6.0; 1.0 mL/min; ca. 20°C
COLUMN:	10 cm × 8-mm octadecylsilylated silica (C18), 5-μm particle size, in Waters RCM-100 radial compression module
CALIBRATION:	standard solution of analytes in methanol
RANGE:	0.3 to 3 μg per sample [1]
ESTIMATED LOD:	0.1 μg per sample [1]
PRECISION (${\overline {S_{t}}}$):	0.06 @ 0.74 to 0.89 μg per sample [1]

ACCURACY

RANGE STUDIED:

not studied

VOL-MIN: -MAX:

30 L @ 10 μg/m³ 500 L

SHIPMENT:

routine

SAMPLE STABILITY:

at least 2 weeks @ 25 °C in the dark [1]

FIELD BLANKS: 2 to 10 field blanks per set

INJECTION VOLUME:

10 μL

MOBILE PHASE: programmed; sodium acetate in acetonitrile/water at pH 6.0; 1.0 mL/min; ca. 20 °C COLUMN:

10 cm × 8-mm octadecylsilylated silica (C18), 5-μm particle size, in Waters RCM100 radial compression module

ACCURACY RANGE STUDIED:

not studied

CALIBRATION:

standard solution of analytes in methanol

BIAS:

not determined

RANGE:

0.3 to 3 μg per sample [1]

OVERALL PRECISION ( ): not determined

ESTIMATED LOD: 0.1 μg per sample [1]

ACCURACY:

PRECISION ( ):

not determined

0.06 @ 0.74 to 0.89 µg per sample [1]

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APPLICABILITY: The working range is 3 to 30 μg/m³ for a 100-L air sample. This method, based on that of Warwick et al. for isocyanates [2], determines 2,4- and 2,6-toluenediamine in air in the presence of isocyanates. Samples from polyurethane foam plants were analyzed simultaneously for 2,4- and 2,6-toluenediamine and 2,4- and 2,6-toluene diisocyanate [1].

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INTERFERENCES: m-Phenylenediamine interferes in the determination of 2,4-toluenediamine.

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OTHER METHODS: Holdren et al. [3] reported a similar method using N-(4-nitrobenzyl)propylamine in toluene for sampling and HPLC with electrochemical detection. Other methods are: (a) absorb on Tenax GC, desorb in toluene, GC [4]; (b) absorb on silica gel, desorb in 2-butanone, GC [5]; (c) sample in aqueous acid, work up, GC of free amines [6] or bis(heptafluoro­ butyryl)amides [7,8]; (d) sample in ethanolic KOH, workup, LC of free amine [9,10] or GC of bis(pentafluoropropionyl) amides [11]; (e) sample with sulfuric acid-coated filter, work up, GC of bis(heptafluorobutyryl)amides [12]. Some of these methods [3,9–11] can be used for the simultaneous determination of toluenediamines and toluene diisocyanates.

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NIOSH Manual of Analytical Methods (NMAM), Fourth Edition