Direct analysis in real time mass spectrometry (DART-MS) was used to characterize commercial polyurethane (PUR) samples without sample pretreatment. More than 50 substances, such as catalysts, stabilizers, antioxidants, flame retardants, plasticizers, chain extenders, chain terminators, polyols, solvents, degradation products and contaminants, a few of them presumably toxic, were detected and identified in 18 PUR items. The identification of 16 compounds was further confirmed by DART MS/MS experiments. Catalysts were the largest class of compounds detected in the PURs by DART-MS. In each of the 18 PUR samples, at least one catalyst residue was identified. In addition, DART-MS was able to detect the migration of hazardous chemicals from the PURs to other objects. The collision-induced dissociation (CID) properties of two PUR catalysts, such as the protonated bis[2-(dimethylamino)ethyl] ether (DMAEE) and the protonated 2,2-dimorpholinodiethylether (DMDEE), as well as those of two PUR antioxidants (Antioxidant 1135 and Antioxidant 1076), were explored.
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Engels HW, Pirkl HG, Albers R, Albach RW, Krause J, Hoffmann A, et al. Polyurethanes: versatile materials and sustainable problem solvers for today’s challenges. Angew Chem Int Ed. 2013;52:9422–41.
Ballesteros-Gómez A, Jonkers T, Covaci A, de Boer J. Screening of additives in plastics with high resolution time-of-flight mass spectrometry and different ionization sources: direct probe injection (DIP)-APCI, LC-APCI, and LC-ion booster ESI. Anal Bioanal Chem. 2016;408:2945–53.
Buchberger W, Stiftinger M. Analysis of polymer additives and impurities by liquid chromatography/mass spectrometry and capillary electrophoresis/mass spectrometry. Adv Polym Sci. 2012;248:39–68.
Paine MRL, Barker PJ, Blanksby SJ. Ambient ionisation mass spectrometry for the characterisation of polymers and polymer additives: a review. Anal Chim Acta. 2014;808:70–82.
Kuki Á, Nagy L, Zsuga M, Kéki S. Fast identification of phthalic acid esters in poly(vinyl chloride) samples by direct analysis in real time (DART) tandem mass spectrometry. Int J Mass Spectrom. 2011;303:225–8.
Crompton TR. Determination of additives in polymers and rubbers. Shawbury: Rapra Technology; 2007.
Cody RB, Laramee JA, Durst HD. Versatile new ion source for the analysis of materials in open air under ambient conditions. Anal Chem. 2005;77:2297–302.
Ackerman LK, Noonan GO, Begley TH. Assessing direct analysis in real-time-mass spectrometry (DART-MS) for the rapid identification of additives in food packaging. Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2009;26:1611–8.
Mess A, Vietzke JP, Rapp C, Francke W. Qualitative analysis of tackifier resins in pressure sensitive adhesives using direct analysis in real time time-of-flight mass spectrometry. Anal Chem. 2011;83:7323–30.
Rothenbacher T, Schwack W. Rapid and nondestructive analysis of phthalic acid esters in toys made of poly(vinyl chloride) by direct analysis in real time single-quadrupole mass spectrometry. Rapid Commun Mass Spectrom. 2009;23:2829–35.
Rothenbacher T, Schwack W. Rapid identification of additives in poly(vinyl chloride) lid gaskets by direct analysis in real time ionisation and single-quadrupole mass spectrometry. Rapid Commun Mass Spectrom. 2010;24:21–9.
Haunschmidt M, Klampfl CW, Buchberger W, Hertsens R. Rapid identification of stabilisers in polypropylene using time-of-flight mass spectrometry and DART as ion source. Analyst. 2010;135:80–5.
Fouyer K, Lavastre O, Rondeau D. Direct monitoring of the role played by a stabilizer in a solid sample of polymer using direct analysis in real time mass spectrometry: the case of Irgafos 168 in polyethylene. Anal Chem. 2012;84:8642–9.
Lebeau D, Ferry M. Direct characterization of polyurethanes and additives by atmospheric solid analysis probe with time-of-flight mass spectrometry (ASAP-TOF-MS). Anal Bioanal Chem. 2015;407:7175–87.
Antal B, Kuki Á, Nagy L, Nagy T, Zsuga M, Kéki S. Rapid detection of hazardous chemicals in textiles by direct analysis in real-time mass spectrometry (DART-MS). Anal Bioanal Chem. 2016;408:5189–98.
Ashida K. Polyurethane and related foams: chemistry and technology. Boca Raton: Taylor & Francis Group; 2006.
Silva Santos L, Henrique Pavam C, Almeida WP, Coelho F, Eberlin MN. Probing the mechanism of the Baylis–Hillman reaction by electrospray ionization mass and tandem mass spectrometry. Angew Chem Int Ed. 2004;43:4330–3.
Abu-Zeid ME, Nofal EE. Effect of catalyst residues on the degradation of rigid foam polyurethane. J Appl Polym Sci. 1986;31:2407–15.
Dix LR, Gardiner DJ, Bradley JR. Studies of degradation in PVC caused by amine additives in polyurethane foam backing, catalysts in polyurethane foams, a one-day seminar. Shropshire: Rapra technology Limited; 1997.
Polyurethane amine catalysts: safe handling guidelines. American Chemistry Council. https://polyurethane.americanchemistry.com/resources-and-document-library/3852.pdf. 2011. Accessed 13 July 2017.
Pohanish RP. Sittig's handbook of toxic and hazardous chemicals and carcinogens 5th edition, volume I: A-H. Norwich: William Andrew Inc.; 2008.
National Center for Biotechnology Information. PubChem Compound Database; CID=8148 https://pubchem.ncbi.nlm.nih.gov/compound/8148. Accessed 13 July 2017.
Ballantyne B. The acute toxicity and irritancy of bis[2-(dimethylamino)ethyl]ether. Vet Hum Toxicol. 1997;39:290–5.
Tsukatani H, Tobiishi K. Determination of N,N-Dimethyldodecylamine and N,N-Dimethyloctadecylamine in river and sea water using liquid chromatography tandem mass spectrometry. Bull Environ Contam Toxicol. 2015;94:801–6.
Ash M, Ash I. Handbook of preservatives. Endicott: Synapse Information Resources Inc.; 2004.
Gill M, Garber MJ, Hua Y, Jenke D. Development and validation of an HPLC–MS–MS method for quantitating bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770) and a related substance in aqueous extracts of plastic materials. J Chromatogr Sci. 2010;48:200–7.
Asimakopoulos AG, Bletsou AA, Wu Q, Thomaidis NS, Kannan K. Determination of benzotriazoles and benzothiazoles in human urine by liquid chromatography-tandem mass spectrometry. Anal Chem. 2013;85:441–8.
Matsukami H, Suzuki G, Takigami H. Compositional analysis of commercial oligomeric organophosphorus flame retardants used as alternatives for PBDEs: concentrations and potential environmental emissions of oligomers and impurities. Environ Sci Technol. 2015;49:12913–21.
European Commission Directive 2014/79/EU. Off J Eur Union. 2014. L 182/49.
European Communities. Directive 2005/84/EC of the European Parliament and of the Council. Off J Eur Union. 2005. L 344:40.
110th United States Congress. Consumer Product Safety Improvement Act (CPSIA). http://www.cpsc.gov/cpsia.pdf. 2008. Accessed 10 Feb 2017.
Camberlin Y, Michaud P, Pesando C, Pascault JP. Isocyanate blocking agents use in polyurethane processing. Macromol Symp. 1989;25:91–9.
"mzCloud.org™, Advanced Mass Spectral Database”, HighChem LLC, Slovakia. https://www.mzcloud.org. Accessed 10 Feb 2017.
Johnson V, Patel SJ, Shah D, Patel KA, Mehta MH. Caprolactam waste liquor degradation by various yeasts. World J Microbiol Biotechnol. 1994;10:524–6.
Brede C, Skjevrak I, Herikstad H. Determination of primary aromatic amines in water food stimulant using solid-phase analytical derivatization followed by gas chromatography coupled with mass spectrometry. J Chromatogr A. 2003;983:35–42.
Pezo D, Fedeli M, Bosetti O, Nerín C. Aromatic amines from polyurethane adhesives in food packaging: the challenge of identification and pattern recognition using quadrupole-time of flight-mass SpectrometryE. Anal Chim Acta. 2012;756:49–59.
Félix JS, Isella F, Bosetti O, Nerín C. Analytical tools for identification of non-intentionally added substances (NIAS) coming from polyurethane adhesives in multilayer packaging materials and their migration into food stimulants. Anal Bioanal Chem. 2012;403:2869–82.
Isella F, Canellas E, Bosetti O, Nerin C. Migration of non intentionally added substances from adhesives by UPLC–Q-TOF/MS and the role of EVOH to avoid migration in multilayer packaging materials. J Mass Spectrom. 2013;48:430–7.
Mortensen SK, Trier XT, Foverskov A, Petersen JH. Specific determination of 20 primary aromatic amines in aqueous food simulants by liquid chromatography–electrospray ionization-tandem mass spectrometry. J Chromatogr A. 2005;1091:40–50.
Cramer GM, Ford RA, Hall RL. Estimation of toxic hazard - a decision tree approach. Food Cosmet Toxicol. 1978;16:255–76.
The work was supported by the GINOP-2.3.2-15-2016-00041 project. The project was co-financed by the European Union and the European Regional Development Fund. Furthermore, this paper was also supported by the János Bolyai Research Scholarship of the Hungarian Academy of Sciences and by the grant K-116465, and supported through the New National Excellence Program of the Ministry of Human Capacities, ÚNKP-16-3 (T. Nagy).
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The authors declare that they have no conflict of interest.
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Kuki, Á., Nagy, L., Nagy, T. et al. Screening of additives and other chemicals in polyurethanes by direct analysis in real time mass spectrometry (DART-MS). Anal Bioanal Chem 409, 6149–6162 (2017). https://doi.org/10.1007/s00216-017-0553-x
- Mass spectrometry