CN104597186A - Gas chromatography-mass spectrometry method for detecting formaldehyde in water-based adhesive - Google Patents

Abstract

The invention discloses a gas chromatography-mass spectrometry method for detecting formaldehyde content in a water-based adhesive. The method comprises the following steps: by utilizing a primary water extraction water-based adhesive containing an internal standard substance, oscillating, extracting, performing centrifugal separation, taking the supernatant, adding a proper amount of PFBHA derivatization reagents, carrying out a derivatization reaction, performing reverse extraction by using normal hexane, performing centrifugal purification, taking the normal hexane liquor, detecting by using gas chromatography/mass spectrometry, performing qualitative detection on the retention time and ion abundance ratio, and performing quantitative detection on characteristic ions. The method disclosed by the invention is simple in pretreatment, easy to operate, high in repeatability and high in recovery rate, and the formaldehyde content in the water-based adhesive can be well accurately measured.

Description

The gas chromatography/mass spectrometry detection method of formaldehyde in a kind of water base adhesive

Technical field

The invention belongs to water base adhesive chemical index detection field, be specifically related to the gas chromatography/mass spectrometry detection method of formaldehyde in a kind of water base adhesive.

Background technology

Formaldehyde is a kind of colourless gas having intense stimulus smell, has the material of higher toxicity, and it is a kind of protoplasm toxin, can make protein coagulating after entering human body, destroys cell protein.Confirmed as possibility carcinogenic substance by Environmental Protection Agency (EPA) at present; I class carcinogen is defined as by the international cancer research institution (IARC) of the World Health Organization (WHO); and point out, formaldehyde can cause the nasopharyngeal carcinoma of the mankind to have had enough evidences to prove.China has also clearly formulated relevant regulation requirement, as GB 9685-2008 " food containers, wrappage adjuvant use hygienic standard ", and GB 2760-2011 " food additives use standard ".And in succession having promulgated GB/T 18883-2002 " Indoor Air Quality standards ", specify the detection method of formaldehyde; The mensuration of formaldehyde in SC/T3025-2006 aquatic products; The mensuration of formaldehyde in SN/T1547-2011 import and export food; The standard method of analyses such as GB/T5009.49-2008 fermented wine and liqueur hygiene standard thereof.The mensuration of the content of formaldehyde reported at present mainly concentrates on the industries such as air, aquatic products, food, environmental protection, furniture, the method adopted has spectrophotometric method, oscilloscopic polarography, the chromatography of ions, liquid phase chromatography, vapor-phase chromatography and By Gas Chromatography-mass Spectrometry.Water base adhesive is by the adhesive that the filmogen that maybe can be dissolved in the water can be disperseed to make, and is also called water-soluble adhesive.The extensively industry such as, printing paper goods aft-loaded airfoil shaping in paper, packaging compound, timber processing, health care.The problem of the aspect such as food packaging safety, domestic environment is subject to people and more and more pays close attention to, and therefore set up a kind of pre-treatment simply, easily operate, method is reproducible, and in the water base adhesive that the recovery is high, the analytical approach tool of content of formaldehyde is of great significance.

Summary of the invention

The object of the present invention is to provide the gas chromatography/mass spectrometry detection method of formaldehyde in a kind of water base adhesive accurately, for the monitoring of water base adhesive safety indexes provides technical support.Detection method provided by the invention, pre-treatment is simple, and easily operate, method is reproducible, and the recovery is high, can better realize the Accurate Determining to content of formaldehyde in water base adhesive.

The technical scheme that the present invention takes is as follows:

A gas chromatography/mass spectrometry detection method for formaldehyde in water base adhesive, is characterized in that: described assay method comprises the steps:

1). water base adhesive is added to containing the deuterated D of internal standard compound ₆the one-level water extraction solution of-acetone, sealing oscillation extraction 1 hour, by oscillation extraction completely sample to hydro-extractor, centrifugal 10min under 3000r/min.

2). accurately pipette the supernatant liquor after centrifugal, add PFBHA derivatization reagent, lucifuge is placed and is carried out derivative reaction 2 hours.

3). derivative sample is completely added normal hexane, oscillation extraction 10min, centrifugal 5min under 3000r/min.

4). use gas chromatograph/mass spectrometer to detect on the normal hexane layer after centrifugal purification, adopt retention time, Selective ion mode qualitative, characteristic ion peak response is quantitative, adopts internal standard method to obtain the content of formaldehyde in water base adhesive.

5). the manufacturing process of typical curve is identical with sample pretreatment process.

6). further, described GC/MS Analysis condition: adopt Rxi-5 capillary separation column (30m × 0.25mm × 0.25 μm) to be separated, injector temperature: 250 DEG C, sample size: 1.0 μ L, split ratio: 10: 1, post flow: 1mL/min, temperature programme: initial temperature 50 DEG C, rise to 180 DEG C with 5 DEG C/min, then rise to 280 DEG C with 25 DEG C/min, retain 5min; Mass Spectrometry Conditions: ionization voltage: 70eV, ion source temperature: 230 DEG C, quadrupole rod temperature: 150 DEG C, solvent delay: 7.5min, scan mode: SIM, formaldehyde and D in water base adhesive ₆after-acetone PFBHA derivatization, quantitative and qualitative selectivity ion is as following table:

Sequence number	Compound title	Retention time	Quota ion	Qualitative ion
					1	Formaldehyde-PFBHA	8.05	181	195
2	D 6-acetone-PFBHA	12.09	259	181

Accompanying drawing explanation

Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further.

Fig. 1 is the standard solution chromatogram of the embodiment of the present invention.

Embodiment

For ease of understanding the present invention, the present invention is described further to provide following examples and accompanying drawing, but the content that the present embodiment is stated is illustrative, should not regard limiting the scope of the invention as.

1. test sample is dissimilar water base adhesive sample, is designated as 1#, 2#, 3#, 4# respectively.

2. test apparatus: 6890N/5975 gas chromatograph-mass spectrometer (GCMS) (Agilent company of the U.S.); Electronic analytical balance (Beijing Sai Duolisi balance company limited, sensibility reciprocal 0.1mg); Stationary liquid is the Rxi-5ms capillary chromatographic column (Restek company of the U.S.) of 5% phenyl/95% dimethyl polysiloxane; Mllipore Q-pod Element ultrapure water generator (Mllipore company of the U.S.); Shaker (Jiangsu Guo Wang experimental apparatus factory), hydro-extractor (German SIGMA company).

3. test reagent and solvent preparation: formaldehyde (Acros Organics company, standard items), D ₆-acetone (Acros Organics company, standard items); PFBHA (Fish Scientific, top grade is pure) normal hexane (Acros Organics company, chromatographically pure).

1). interior mark liquid extract: the 1mg/mLD pipetting 0.5mL ₆-acetone (standard items), in 500mL volumetric flask, is settled to scale with one-level water, obtains the extract of 1mg/L.

2). formaldehyde standard solution: pipette the 1000mg/mL formaldehyde standard items of 1mL in 50mL volumetric flask, in adopting, mark extract constant volume, obtains formaldehyde mother liquor.Pipette the above-mentioned formaldehyde mother liquor of different volumes respectively, be made into interior mark extract the six grade standard solution that concentration is 0.05mg/mL, 0.1mg/mL, 0.2mg/mL, 0.5mg/mL, 1mg/mL, 5mg/mL.

4. the gas chromatography/mass spectrometry detection method of formaldehyde in water base adhesive, comprises the following steps: described assay method comprises the steps:

1). accurately take 0.2g water base adhesive sample, be added to containing the deuterated D of internal standard compound ₆in the 10mL one-level water extraction solution centrifuge tube of-acetone, sealing oscillation extraction after 1 hour, by oscillation extraction completely solution to hydro-extractor, centrifugal 10min under 3000r/min.

2). accurately pipetting the supernatant 5ml through extracting, adding the 20mg/mLPFBHA derivatization reagent of 100 μ l in another centrifuge tube of 15ml, lucifuge derivatization 2 hours.

3). derivative solution is completely added 2ml normal hexane, oscillation extraction 10min, and centrifugal 5min under 3000r/min, carries out centrifuging purification.

4). the manufacturing process of typical curve is identical with sample pretreatment process.

5). use gas chromatograph/mass spectrometer to detect on the normal hexane layer after centrifugal purification, adopt retention time, Selective ion mode qualitative, characteristic ion peak response is quantitative, adopts internal standard method to obtain the content of formaldehyde in water base adhesive.

6). GC/MS Analysis condition: adopt Rxi-5 capillary separation column (30m × 0.25mm × 0.25 μm) to be separated, injector temperature: 250 DEG C, sample size: 1.0 μ L, split ratio: 10: 1, post flow: 1mL/min, temperature programme: initial temperature 50 DEG C, rises to 180 DEG C with 5 DEG C/min, rise to 280 DEG C with 25 DEG C/min again, retain 5min; Mass Spectrometry Conditions: ionization voltage: 70eV, ion source temperature: 230 DEG C, quadrupole rod temperature: 150 DEG C, solvent delay: 7.5min, scan mode: SIM, formaldehyde and D in water base adhesive ₆after-acetone PFBHA derivatization, quantitative and qualitative selectivity ion is as following table:

Sequence number	Compound title	Retention time (min)	Quota ion	Qualitative ion
					1	Formaldehyde-PFBHA	8.05	181	195
2	D 6-acetone-PFBHA	12.09	259	181

5. method detectability and quantitative limit: with the standard model continuous sample introduction 10 times of least concentration, record concentration value statistical standard deviation, detectability is obtained with 3 times of standard deviations, and quantitative limit is obtained with 10 times of standard deviations, and the detection of this method formaldehyde is limited to 0.12mg/kg; Quantitatively be limited to 0.39mg/kg, show that the sensitivity of this method is higher.

6. the calculating of content of formaldehyde in water base adhesive: to 4 water base sample tests, each sample re-treatment 3 times, and recovery experiment is done to each water base adhesive sample, calculate its RSD% and recovery %.

In upper table result display formaldehyde RSD% be 3.62%-5.27%, the recovery is 97.5%-104.7%, show the inventive method reproducible, the recovery is higher, meets quantitative test requirement.

Claims (3)

1. the gas chromatography/mass spectrometry detection method of formaldehyde in water base adhesive, is characterized in that, comprise the following steps:

1). water base adhesive is added to containing the deuterated D of internal standard compound ₆the one-level water extraction solution of-acetone, sealing oscillation extraction 1 hour, by oscillation extraction completely sample to hydro-extractor, centrifugal 10min under 3000r/min;

2). pipette the supernatant liquor after centrifugal, add PFBHA derivatization reagent, lucifuge is placed and is carried out derivative reaction 2 hours;

3). derivative sample is completely added normal hexane, oscillation extraction 10min, centrifugal 5min under 3000r/min;

4). use gas chromatograph/mass spectrometer to detect on the normal hexane layer after centrifugal purification, adopt retention time, Selective ion mode qualitative, characteristic ion peak response is quantitative, adopts internal standard method to obtain the content of formaldehyde in water base adhesive.

2. the gas chromatography/mass spectrometry detection method of formaldehyde in water base adhesive according to claim 1, is characterized in that: the manufacturing process of typical curve is identical with sample pretreatment process.

3. the gas chromatography/mass spectrometry detection method of formaldehyde in water base adhesive according to claim 1, it is characterized in that: described GC/MS Analysis condition: adopt Rxi-5MS capillary column (30m × 0.25mm × 0.25 μm) to be separated, injector temperature: 250 DEG C, sample size: 1.0 μ L, split ratio: 10: 1, post flow: 1mL/min, temperature programme: initial temperature 50 DEG C, rise to 180 DEG C with 5 DEG C/min, then rise to 280 DEG C with 25 DEG C/min, retain 5min; Mass Spectrometry Conditions: ionization voltage: 70eV, ion source temperature: 230 DEG C, quadrupole rod temperature: 150 DEG C, solvent delay: 7.5min, scan mode: SIM, formaldehyde and D in water base adhesive ₆after-acetone PFBHA derivatization, quantitative and qualitative selectivity ion is as following table:

Sequence number Compound title Retention time Quota ion Qualitative ion 1 Formaldehyde-PFBHA 8.05 181 195 2 D ₆-acetone-PFBHA 12.09 259 181