纺织品中甲醛测量

1、DETERMINATION OF FREE FORMALDEHYDE ON TEXTILE SUBSTRATE BY HPLCBojana VONCINAUniversity of Maribor, Textile Department Smetanova 17, 2000 Maribor, SloveniaITSAPT seminar, Guimaraes, November 2005Formaldehyde is built in the atmosphere thought photochemical processes of hydrocarbonsIt is produced dur

2、ing the uncompleted combustion of wood, oil, gas, tobaccoSource of formaldehyde: - Automobiles and airplanes70-80%- Heating and incineration 13-15%- Formaldehyde in chem. prod.1%ITSAPT seminar, Guimaraes, November 2005Formaldehyde is found in human body as a building blocks for amino acids and prote

3、insBlood2-3 mg/kgApple 17-22 mg/kgTomatoes6-7 mg/kgWood4-18 mg/kgFormaldehyde is often used as a building block for a number of important chemical products, intermediates and consumer goods: - urea-formaldehyde resins (25%), - phenol- formaldehyde resins (20%), - plastics (15%), - intermediates (22%

4、). ITSAPT seminar, Guimaraes, November 2005Toxicity DataFormaldehyde is readily absorbed through skin and is toxic byinhalation It is considered toxic, carcinogen, mutagen, corrosiveHealth Effects:Inhalation: formaldehide is extremely destructive to tissue of the mucous membranes and that of the upp

5、er respiratory tract. Inhalation may be fatal as a result of spasm and inflammation. Eyes/Skin: extremely destructive to the tissue of the eyes and skin. Can cause allergic skin reactionsIngestion: Can cause gastrointestinal disturbances. May alter genetic material. This is considered a carcinogen.T

6、arget Organs: eyes, kidneys, liver, heart, potential cancer agent, testis, ovariesITSAPT seminar, Guimaraes, November 2005The most effective crosslinking reagents for durable press finishing of cellulose fibers are formaldehyde adducts of urea which release formaldehyde during the production and wea

7、ring of in such way treated clothesFormaldehyde durable press finishers are applied to the textile substrate mainly in the form of N-methylol and N-alkoxymethyl compounds ITSAPT seminar, Guimaraes, November 2005Release of formaldehyde from the textile substrate can be measured by:STANDARD TEST METHO

8、DSJapan Law 112 (EN ISO 14184-1)AATCC-112The formaldehyde content below 20 mg/kg can not be shown to be caused by the formaldehyde which was released by the crosslinking reagent. ALTERNATIVE TEST METHODS edana recommended test method using HPLCHPLCITSAPT seminar, Guimaraes, November 2005EN ISO 14184

9、-1 standard test methodStandard solutions of formaldehyde with concentration levels of 0.3, 0.6, 0.9, 3.0, 6.0, 15.0 and 30.0 mg/L in the 3,5, - diacetyl 1,4-dihydrolutidin forms were prepared. The formaldehyde derivative solutions were prepared in water and in matrix (extract from untreated cotton

10、fibers). Six replicates of each concentration level were preparedFrom the textile substrateformaldehyde was extracted with water at 40C, filtered and then converted by using acetyl-acetone reagent to yellow colored compoundITSAPT seminar, Guimaraes, November 2005Validation of absorbance measurements

11、 on UV/VisWith Grubbs and Beck statistical test were shown that there were no aberrant valuesAn F test was applied to check heteroscedasticity: standard deviation increase with the concentrationCorrelation coefficient for standard water and matrix solutions was greater than 0.99Quality coefficient (

12、QC) was lower than permitted 5%Anova test shows that the experimental error was smaller than lack of fit (LOF) for the linear calibration curve Precision of standard water and matrix solutions was better than 10% The limit of detection (LOD) was 0.628 mg/lThe limit of quantification (LOQ) was 1.197

13、mg/l The amount of formaldehyde extracted for each sample can be calculated by:Konc (x) = 7,493 ABS - 0,06356ITSAPT seminar, Guimaraes, November 2005Free formaldehyde measured by HPLC Standard water and matrix solutions of formaldehyde with concentrations levels 0.075, 0.15, 0.3, 0.6, 0.9, 3.0, 6.0,

14、 15.0 and 30.0 mg/L in the 3,5, - diacetyl 1,4-dihydrolutidin forms were preparedFormaldehyde was extracted from textile substrate with water at 40C, filtered and then converted by using acetylacetone reagent to yellow colored compoundHPLC Varian Prostar 210 pump,Varian Prostar 310 UV/Vis detector (

15、at 410 nm), STAR Chromatography Workstation Varian 4.5,LiChrosorb RP-18 coloum with particle size 7 m,ITSAPT seminar, Guimaraes, November 2005Validation of the HPLC analytical methodThe optimisation of the method (the proper column, mobile phase, solvents, temperature of the column etc.) was done. T

16、he concentration of free formaldehyde in the aqueoussolution was determined usingpeak areas from the standardand sample chromatograms. Mobile phase methanol-water (70:30 v/v).The retantion time for formaldehyde derivative was 2.7 min ITSAPT seminar, Guimaraes, November 2005Validation of the HPLC ana

17、lytical methodWith Grubbs and Beck statistical test were shown that there were no aberrant valuesAn F test was applied to check heteroscedasticity: standard deviation increase with the concentrationCorrelation coefficient for standard water and matrix solutions was greater than 0.99Quality coefficie

18、nt (QC) was lower than permitted 5%Anova test shows that the experimental error was smaller than lack of fit (LOF) for the linear calibration curvePrecision of standard water and matrix solutions was better than 10% The limit of detection (LOD) was 0.0199 mg/lThe limit of quantification (LOQ) was 0.

19、066 mg/l The amount of formaldehyde extracted for each sample can be calculated by:Konc (x) = 0,2055 * 10-4 AREA 0,222ITSAPT seminar, Guimaraes, November 2005CONCLUSIONS The results obtained by the standard test method, JapanLaw112, were compared with the results obtained by HPLCmethod where separat

20、ion was performed on RP C 18 column with water-MeOH as a mobile phase. The limit of detection (LOD) for Japan Law 112 was 0.628 mg/l and the limit of quantification (LOQ) was 1.197 mg/l The limit of detection (LOD) for HPLC method was 0.0199 mg/l and the limit of quantification (LOQ) was 0.066 mg/l

21、Matrix has no influence on the formaldehyde content in the analysed solution. ITSAPT seminar, Guimaraes, November 2005FORMALDEHYDE IN MICROENCAPTULATED TEXTILE MATERIALSBojana VONCINAUniversity of Maribor, Textile Department Smetanova 17, 2000 Maribor, SloveniaITSAPT seminar, Guimaraes, November 200

22、5IntroductionEssential oils from plants Lavandula sp.(lavender), Rosmarinus sp (rosemary) andSalvia sp. (sage) are natural fungicide andantibacterial agents. These oils were microencapsuled in melamine-formaldehyde microcapsules and cross linked onPES nonwoven textile materials.Such textile material

23、 is capable ofreleasing formaldehyde by decompositionof microcapsules.ITSAPT seminar, Guimaraes, November 2005Sources of the formaldehyde Textile material (PES) cross-linking reagent microcapsules wall : melamine-formaldehyde resins core :25 % mixture of essential oils, 75 % solvent 80 % mixture of

24、essential oils, 20 % solvent mixture of essential oils: - lavender 70 % - rosemary 20 % - sage 10 % solvent: isopropyl mirystate ITSAPT seminar, Guimaraes, November 2005ExperimentalRelease of formaldehyde from the textile substrate was determined by EN ISO 14184-1 (Japan Law 112 method),AATCC test 1

25、12-1998,HPLC method, where the separation was achieved with elution using methanol-water, as eluents on a reverse phase column and was monitored at 410 nm with a UV/VIS detector. In all three methods the extracted formaldehyde was converted by using acetylacetone reagent to yellow coloured compound.

26、 ITSAPT seminar, Guimaraes, November 2005The formaldehyde contents were determined in different textile samples:a)untreated textile material (PES nonwoven)b) textile material with cross-linking reagent (suspension of latex and acrilate emulsifier)c) textile material with empty microcapsules,d)textil

27、e material with cross-linkinked empty microcapsules,e) textile material with cross-linked microcapsules filled with oils (25 % mixture of essential oils, 75 % solvent) f) textile material with cross-linked microcapsules filled with oils (80 % mixture of essential oils, 20 % solvent)The formaldehyde

28、contents were determine also in mixture of oils and pure rosemary and sage oil.ITSAPT seminar, Guimaraes, November 2005 Untreated textile material and cross-linking reagent do not contain formaldehyde (7 mg/kg). Microcapsules walls contribute to the amount of of the formaldehyde significantly: The a

29、verage formaldehyde content for the microencaptulated textile material with empty microcapsules is 715 mg/kg and 766 mg/kg for microencaptulated textile material with microcapsules filled with oils (both results are obtained by Japan Law method). Results from AATCC test for the same samples are 5.12

30、6 mg/kg and 4.174 mg/kg respectively.Results and conclusionsITSAPT seminar, Guimaraes, November 2005Results obtained by HPLC method: indicate that only formaldehyde is released from the textile samples microencaptulated with and without essential oil. Although some amount of formaldehyde is proved i

31、n pure essential oils, amount of essential oil which is applied on textile material with microcapsules (160 g/m2) contribute very little to total amount of formaldehyde. This was proved by the measurements of released formaldehyde after the mechanical damages of microcapsules on the textile substrate ITSAPT seminar, Guima