CN103728405B - The research method of timber preservative Transport in a kind of Wood children articles for use - Google Patents
The research method of timber preservative Transport in a kind of Wood children articles for use Download PDFInfo
- Publication number
- CN103728405B CN103728405B CN201310721822.4A CN201310721822A CN103728405B CN 103728405 B CN103728405 B CN 103728405B CN 201310721822 A CN201310721822 A CN 201310721822A CN 103728405 B CN103728405 B CN 103728405B
- Authority
- CN
- China
- Prior art keywords
- sample
- wood
- preservative
- transport
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention discloses the research method of timber preservative Transport in a kind of Wood children articles for use, comprise the steps: that (1) takes wood sample top layer 3mm thickness, ground instrument is ground into less than 2mm wood flour, the total content of every kind of preservative in mensuration sample；(2) measure the migration amount of every kind of preservative in sample: add in the sample and migrate solution, add internal standard working solution, use gas chromatogram tandem mass spectrum detection method to measure；(3) based on to the total content of every kind of preservative in sample and the mensuration of migration amount, the result obtained is analyzed, draws maximum mobility and the Transport of timber preservative in Wood children articles for use under different experiments simulated conditions.Research method of the present invention more has theoretical foundation for the Transport experimental design of 10 kinds of timber preservatives, is more beneficial for the making of positive criteria sample, ensures the result of study of Transport the most simultaneously.
Description
Technical field
The present invention relates to the research method of preservative Transport in a kind of timber, particularly relate to a kind of for Wood children articles for use
The research method of middle timber preservative Transport.
Background technology
The most common Wood children articles for use have wooden toy, infanette etc..Due to the report of the poisonous event of Toys paint coat, mesh
Front a lot of producers declare its product " log ", " non-toxic paint ", to the impression of a kind of environment-protecting asepsis of consumer, but, by wherein may be used
The harm that the timber preservative that can exist is brought often is ignored by people.For avoiding the occurrence of the situation such as mouldy that ftractures because making moist, log
Timber and finished product the most all can be through preservative treatments.As a example by wooden toy, the infant of less than 3 years old when playing, Chang Huiyong
Mouth is stung or is licked and licks, or is immersed in water by toy, and such timber preservative can move to baby along with saliva, perspiration or water
In child's body, it is worked the mischief, as polystream aldehydes matter and pyrethrin may teratogenesis, carcinogenic and cause gene mutation
Deng.10 kinds of timber preservatives referred to herein, in toy harmonized stndard EN71-9 announced, are carried out in 10,11 by European Union
Limitation requirement, minimum limitation is 1mg/kg.
Transport for timber preservative is studied, and the work carried out the most both at home and abroad is considerably less, it is possible to the data found only relates to
And waterborne preservative and the pentachlorophenol such as CCA, for sample be mainly soil and subsoil water.Researcher is to plastics both at home and abroad
Etc. the transfer behavior of the materials such as plasticizer, bis-phenol, aromatic amine, ultraviolet absorber in packaging material for food, there are reports, but
Due to product substrate, use environment, research material object the most different, existing achievement in research can not directly be applied mechanically.
Compared with Transport, the polystream phenols detection method report residual with chrysanthemum esters agriculture is relative more, for mainly
Food, environmental sample etc..Due to the complicated component of wood sample, being combined only with chromatography or chromatograph-single-stage mass spectrometry may not
Enough selectivitys and sensitivity are provided, and tandem mass spectrum has high selectivity and highly sensitive feature, it is possible at complex matrices
In trace materials is carried out confirmatory analysis, the most suitable for studying the Transport of material as detection technique.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of easy and simple to handle, timber preservative in Wood children articles for use accurately and reliably
The research method of Transport.
In a kind of Wood children articles for use, the research method of timber preservative Transport, comprises the steps:
(1) contained the positive criteria sample of 10 kinds of timber preservatives by self-control, measure sample by gas chromatography tandem mass spectrometry method
In the actual total content of every kind of preservative；
(2) the migration amount of every kind of preservative in positive is measured: cut wood sample top layer 3mm thickness with low speed cutting machine,
Ground instrument is ground into less than 2mm wood flour, accurately weighs 2g sample and fills in test tube in 50mL tool, adds and migrate solvent 40
ML, described migration solvent is simulation saliva, simulated sweat or water, 37 DEG C, water-bath vibration 1～10h under the conditions of 100r/min
Rear mistake 200 μm rustless steel screen, obtains migration solution；1mL internal standard working solution is added, by pH in described migration solution
Value is adjusted to 6, adds 1mL acetic anhydride and performs the derivatization, and operates about 1min and is placed on shaking table vibration 10min；After derivatization
Solution by activating through 5mL methanol in advance, the Oasis HLB solid-phase extraction column of 5mL deionized water balance, through 5mL
Deionized water drip washing, utilizes vacuum pump to be drained by water, finally with 10mL ethyl acetate eluting, collects eluent and adds appropriate nothing
Aqueous sodium persulfate is dried, and uses gas chromatography tandem mass spectrometry detection method to measure after vortex 30s；
(3) for the handling characteristics of Wood children articles for use, by setting different experimental simulation conditions, based on in sample every kind
The total content of preservative and the mensuration of migration amount, collect the result obtained and analyze, and draws in Wood children articles for use every kind
The maximum mobility of timber preservative and Transport.
The research method of timber preservative Transport in Wood children articles for use of the present invention, wherein said method measures simultaneously
The total content of 10 kinds of antiseptic substance and migration amount in sample, and carry out Transport research by experimental simulation condition, described
Preservative is 2,4 chlorophenesic acids, 2,4,5-trichlorophenol, 2,4,6,-T, 2,4,6-trichlorophenol, 2,4,6,-T, 2,3,4,6-tetrachlorophenol, gamma hch, pentachloro-
Phenol, cypermethrin, cyfloxylate, Permethrin and decis.
The research method of timber preservative Transport in Wood children articles for use of the present invention, wherein step (3) specifically includes
Following steps: for polystream aldehydes matter, prepare 5mg/kg and 10mg/kg positive criteria sample, for pyrethrin
Preparation 50mg/kg and 100mg/kg positive, migrates 1～10h respectively in different migration solvents, and bath temperature is set to
37 DEG C, separately sampled mensuration each material migration amount under the conditions of simulation experiment, result collects mapping, intuitively enters transfer behavior
Row is analyzed；By 10 kinds of actual total contents of material in all positive are measured, it is calculated migration numerical quantity with corresponding
The ratio of total numerical quantity, the most each material mobility in 10h, the most each material maximum of mobility in 10h is
Maximum mobility, by comparing each material maximum mobility in difference migrates solvent in the positive of different content, and with
Result before compares, and finally draws the Transport of 10 kinds of timber preservatives.
In Wood children articles for use of the present invention, the research method of timber preservative Transport, also includes the preparation of positive,
Comprise the steps: blank wood sample beveller is ground into the wood flour less than 2mm, weigh appropriate wood flour in tool plug circle
In end flask, a conical flask adds complete mixed standard solution, and adds methanol dilution, it is ensured that the solution after dilution pours round bottom into
Can be by whole wood flour submergences in flask；Stand overnight after round-bottomed flask is placed in shaking table vibration 2h, it is ensured that preservative fully permeates
To wood internal, then 35 DEG C, the steaming of 170hPa backspin, during rotation is steamed, pressure is gradually transitions 170hPa by 300hPa,
By solvent slow evaporation near dry, the most dry sawdust sample is laid on big surface plate, until solvent volatilizees completely, i.e. obtains
Positive.
The research method of timber preservative Transport in Wood children articles for use of the present invention, wherein said internal standard working solution
Being prepared from by the following method: weigh 50mg2,3,4-trichlorophenol, 2,4,6,-Ts, in 100mL brown volumetric flask, are 9:1 by volume ratio
Ethanol/glacial acetic acid solution constant volume, be configured to the internal standard storing solution of 500mg/L, being then diluted to concentration is 5mg/L's
Internal standard working solution.
The research method of timber preservative Transport in Wood children articles for use of the present invention, the system of wherein said simulation saliva
Preparation Method is prepared from by the following method: weigh sodium chloride 4.5g, potassium chloride 0.3g, sodium sulfate 0.3g, ammonium chloride 0.4 respectively
G, 90% lactic acid 3.0g, carbamide 0.2g, it is settled to 1000mL, pH ≈ 3 with deionized water after mixing；
Described simulated sweat is prepared from by the following method: weigh sodium bicarbonate 4.2g, sodium chloride 0.5g, potassium carbonate 0.2g respectively,
It is settled to 1000mL, pH ≈ 8.8 with deionized water after mixing.
The research method of timber preservative Transport in Wood children articles for use of the present invention, wherein step (1) specifically includes
Following steps: by sample comminution to less than 2mm wood flour, accurately weigh 2g, by methanol supersound extraction 2 times, each 20mL,
Extract 15min, in filtration also merging filtrate to centrifuge tube, add 1mL internal standard working solution, at 4 DEG C, 13000r/min
Under the conditions of centrifugal 5min, be transferred in Cor Gigeriae Galli bottle after 0.45 μm PTFE membrane filtration, 35 DEG C, 170hpa backspin inspissation
It is reduced to 2mL, in concentrated solution, adds 40mL0.1mol/L solution of potassium carbonate, add 1mL acetic anhydride after shaking up and perform the derivatization,
Exitting in vibration limit, limit, operates about 1min and be placed on shaking table vibration 10min, by the solution after derivatization by advance through 5mL first
Alcohol activation, the Oasis HLB solid-phase extraction column of 5mL deionized water balance, through 5mL deionized water drip washing, utilize vacuum pump
Water is drained, finally with 10mL ethyl acetate eluting, collects the eluent appropriate anhydrous sodium sulfate of addition and be dried, after vortex 30s
Gas chromatography tandem mass spectrometry detection method is used to measure.
The research method of timber preservative Transport in Wood children articles for use of the present invention, wherein said gas chromatogram-series connection
The chromatography-mass spectroscopy condition of Mass Spectrometry detection method is: Agilent HP-5MS chromatographic column, and specification is 30m × 0.25mm i.d., 0.25
μm；Injector temperature 280 DEG C；Flow rate of carrier gas is 1.0mL/min；Splitless injecting samples, sample size 2 μ L；Temperature programming: just
Beginning temperature 60 C, rises to 200 DEG C with 20 DEG C/min, then rises to 280 DEG C with 10 DEG C/min and keeps 8min；Solvent
Postpone 5min；Transmission line temperature 250 DEG C；Ion source temperature 180 DEG C；EI ionizes mode, ionizing energy 70eV, MRM
Pattern measures.
In Wood children articles for use of the present invention, the research method difference from prior art of timber preservative Transport is:
Described method is based on the organophosphorous pesticides-tandem mass spectrum of 10 kinds of timber preservatives in Wood children articles for use
(SPE-GC-MS/MS) detection technique, it is proposed that the assay method of a kind of new timber preservative migration amount, can survey simultaneously
Measure 10 kinds of polystream phenols in sample and chrysanthemum esters antiseptic content and migration amount.Further, (1) wood sample is taked specific
Sampling mode so that migrate experimental design more have theoretical foundation, be more beneficial for the making of positive criteria sample simultaneously.Pass through
Design and counter push away experiment, under the conditions of timber preservative is internally migrated the long period with simulation saliva by wood surface, timber top layer 3
In mm, wood preservation agent content is far longer than inside, when thus release actually occurs transfer behavior, and mainly timber top layer 3mm
Interior timber preservative migrates out, therefore desirable top layer 3mm during sampling.(2) solution generation derivative reaction pH value is migrated
Setting, owing to the character of polystream phenols and chrysanthemum esters timber preservative material differs widely, use the many chlorine of gas Chromatographic Determination
Phenol type substances needs first to carry out acetic anhydride derivatization in solution of potassium carbonate medium.And after migration test completes, Jie of derivatization
Matter is simulation saliva, simulated sweat or water, and this research method, by carefully optimizing, is determined by the response rate and prevents for 10 kinds of timber
The derivatization pH value that rotten agent is optimal, finds in research that the variation of this value has a significant impact for whole result of study.
For the handling characteristics of Wood children articles for use, by setting different experimental simulation conditions, based on to every kind of anticorrosion in sample
The total content of agent and the mensuration of migration amount, collect the result obtained and analyze, and draws wood preservation in Wood children articles for use
The maximum mobility of agent and Transport.
For 10 kinds of timber preservatives, prepare the positive criteria sample of different content, in migrating solution, migrate 1～10h respectively,
Bath temperature is set to 37 DEG C, and separately sampled mensuration each material migration amount under the conditions of simulation experiment, result collects mapping, can be straight
See and transfer behavior is analyzed, the factor affecting Transport is inquired into.By in above-mentioned all positive 10 kinds
The actual total content of material is measured, and makees ratio with all of migration numerical quantity with corresponding total numerical quantity, show that each material is at 10h
Interior mobility.The most each material maximum of mobility in 10h is maximum mobility, by comparing the sun of different content
Property sample in each material migrate the maximum mobility in solution in difference, and mutually confirm with result before, finally draw 10 kinds
The Transport of timber preservative.
In Wood children articles for use of the present invention, the research method of timber preservative Transport is for target in the wood sample of complex matrices
Thing total amount and the mensuration of migration amount, have good selectivity and sensitivity, easy and simple to handle, effect is obvious.For 10 kinds of timber
The Transport experimental design of preservative more has theoretical foundation, is more beneficial for the making of positive criteria sample, ensures to migrate rule simultaneously
The result of study of rule is the most accurately and reliably.
Below in conjunction with the accompanying drawings the research method of timber preservative Transport in the Wood children articles for use of the present invention is made furtherly
Bright.
Accompanying drawing explanation
Fig. 1 is 10 kinds of timber preservative marks in the research method of timber preservative Transport in Wood children articles for use of the present invention
The MRM chromatogram of quasi-solution；The preservative kind that numbering represents is identical with table 1；
Fig. 2 be in Wood children articles for use of the present invention in the research method of timber preservative Transport 10 kinds of timber preservatives by
The experimental result schematic diagram that simulation saliva migrates to wood internal；Wherein, A:0～3mm;B:3～6mm;C: residue timber sample
Product；
Fig. 3 is different pH value Imitating salivas in the research method of timber preservative Transport in Wood children articles for use of the present invention
The schematic diagram of the relative recovery of 10 kinds of materials in liquid；
Fig. 4 is different pH value Imitating antiperspirant in the research method of timber preservative Transport in Wood children articles for use of the present invention
The schematic diagram of the relative recovery of 10 kinds of materials in liquid；
Fig. 5 is that in Wood children articles for use of the present invention, in the research method of timber preservative Transport, 10 kinds of timber preservatives exist
Migration results schematic diagram under the conditions of 37 DEG C.
Detailed description of the invention
Embodiment 1
The research method of timber preservative Transport in a kind of Wood children articles for use, it is characterised in that: comprise the steps:
One, preliminary preparation
1, instrument and reagent
7890A gas chromatograph (Agilent company of the U.S.)；(U.S. Waters is public for Quattro Micro triple level Four bar mass spectrum
Department)；Solid-phase extraction device (Supelco company of the U.S.)；NVC-2000 type Rotary Evaporators (Eyela company of Japan)；SM2000
Type cutting and grinding instrument (Retsch company of Germany)；TechCut4 low speed cutting machine, joins micro-rack saw sheet (Allied company of the U.S.)；
NTS-4000 water bath with thermostatic control agitator (Eyela company of Japan)；Oasis HLB solid-phase extraction column (6mL, 200mg, the U.S.
Waters company).
Standard substance: 2,4,5-trichlorophenol, 2,4,6,-T, 2,4,6-trichlorophenol, 2,4,6,-T, 2,3,4 trichlorophenol, 2,4,6,-Ts, 2,3,4,6-tetrachlorophenol, gamma hch,
Cypermethrin, cyfloxylate, decis are purchased from Accustandard company, purity >=98%；Pentachlorophenol, 2,4 2
Chlorophenol is purchased from Dr.Ehrenstorfer company, purity >=99%；Permethrin is purchased from Fluka company, purity >=98%；Wherein, chlorine
Chrysanthemum ester, cypermethrin, cyfloxylate are the mixture of isomer.Experimental water is the deionization prepared through Milli-Q system
Water；Helium, argon (＞ 99.999%)；In experiment, the ethanol of use, acetic acid, acetic anhydride are analytical pure, and other reagent is
Chromatographically pure.
2, the preparation of solution
Test substance: weigh 10 kinds of each 100mg of preservative standard substance in 100mL brown volumetric flask, with 9:1(v/v) second
Alcohol/glacial acetic acid solution constant volume, is configured to the list mark storing solution that concentration is 1000mg/L, and utilizing single mark storing solution configuration concentration is 100
The complete mixed storing solution of mg/L.In experiment as required, available 9:1(v/v) ethanol/glacial acetic acid be diluted to the series of desired concn
Working solution.
Internal standard material: weigh 50mg2,3,4-trichlorophenol, 2,4,6,-Ts are in 100mL brown volumetric flask, with 9:1(v/v) ethanol/ice vinegar
Acid solution constant volume, is configured to the internal standard storing solution of 500mg/L, is then diluted to the internal standard work that concentration is 5mg/L molten
Liquid.
Simulation saliva: sodium chloride 4.5g, potassium chloride 0.3g, sodium sulfate 0.3g, ammonium chloride 0.4g, 90% lactic acid 3.0g, urine
Element 0.2g, deionized water is settled to 1000mL, pH ≈ 3.Simulated sweat: sodium bicarbonate 4.2g, sodium chloride 0.5g, carbonic acid
Potassium 0.2g, deionized water is settled to 1000mL, pH ≈ 8.8.
3, the making of positive
Blank wood sample beveller is ground into the wood flour less than 2mm, weighs appropriate wood flour in tool plug round-bottomed flask,
In a conical flask, add appropriate complete mixed standard solution, and add proper amount of methanol dilution, it is ensured that the solution after dilution is poured round bottom into and burnt
Can be by whole wood flour submergences in bottle.Stand overnight, to guarantee that preservative fully permeates after round-bottomed flask is placed in shaking table vibration 2h
To wood internal.Then 35 DEG C, 170hPa(be gradually transitions 170hPa by 300hPa, to avoid solution bumping) under
Rotation is steamed, by solvent slow evaporation near dry.The most dry sawdust sample is laid on big surface plate, until solvent volatilizees completely,
I.e. obtain positive.
Two, assay method
(1) total amount of every kind of preservative in mensuration sample:
By sample comminution to less than 2mm wood flour, accurately weigh 2g, with methanol supersound extraction 2 times, each 20mL, extract
15min.Filter and merging filtrate be in centrifuge tube, add 1mL internal standard working solution, 4 DEG C, under the conditions of 13000r/min
Centrifugal 5min, is transferred in Cor Gigeriae Galli bottle after 0.45 μm PTFE membrane filtration, 35 DEG C, 170hpa backspin inspissation be reduced to 2mL.
In concentrated solution, add 40mL0.1mol/L solution of potassium carbonate, add 1mL acetic anhydride after shaking up and perform the derivatization, vibration limit, limit
Venting, operates about 1min and is placed on shaking table vibration 10min.By the solution after derivatization by activating through 5mL methanol in advance,
The Oasis HLB solid-phase extraction column of 5mL deionized water balance, through 5mL deionized water drip washing, utilizes vacuum pump to be drained by water,
Finally with 10mL ethyl acetate eluting, collecting the eluent appropriate anhydrous sodium sulfate of addition and be dried, after vortex 30s, upper machine measures.
(2) the migration amount of every kind of preservative in mensuration sample:
Cutting wood sample top layer 3mm thickness with low speed cutting machine, ground instrument is ground into less than 2mm wood flour, accurately weighs
2g sample, in 50mL tool plug test tube, adds and migrates solvent 40mL, 37 DEG C, water-bath vibration (1～10 under the conditions of 100r/min
H) cross 200 μm rustless steel screens afterwards, obtain migration solution.1mL internal standard working solution is added, by pH value in migrating solution
It is adjusted to 6, adds 1mL acetic anhydride and perform the derivatization, operate about 1min and be placed on shaking table vibration 10min.After derivatization
Solution by activating through 5mL methanol in advance, the Oasis HLB solid-phase extraction column of 5mL deionized water balance, through 5mL go from
Sub-water wash, utilizes vacuum pump to be drained by water, finally with 10mL ethyl acetate eluting, collects eluent and adds appropriate anhydrous sulfur
Acid sodium is dried, and after vortex 30s, upper machine measures.
Wherein, chromatography-mass spectroscopy condition particularly as follows:
Agilent HP-5MS chromatographic column (30m × 0.25mm i.d., 0.25 μm)；Injector temperature 280 DEG C；Flow rate of carrier gas is
1.0mL/min；Splitless injecting samples, sample size 2 μ L；Temperature programming: initial temperature 60 DEG C, rises to 200 DEG C with 20 DEG C/min,
Then 280 DEG C (keeping 8min) are risen to 10 DEG C/min；Solvent delay 5min；Transmission line temperature 250 DEG C；Ion source temperature
Spend 180 DEG C；EI ionizes mode, and ionizing energy 70eV, MRM pattern measures.
(3) for the handling characteristics of Wood children articles for use, by setting different experimental simulation conditions, based on in sample every kind
The total content of preservative and the mensuration of migration amount, collect the result obtained and analyze, and draws timber in Wood children articles for use
The maximum mobility of preservative and Transport.
Three, result and analysis
1, the total quantity measuring method of timber preservative
Based on SPE-GC-MS/MS technology, the present invention establishes and measures these 10 kinds of timber preservatives in Wood children articles for use simultaneously
Method.Result shows, method, for the detection of object in the wood sample of complex matrices, has good selectivity and spirit
Sensitivity.Under the conditions of chromatographic mass spectrometry of the present invention, the typical chromatographic fractionation figure of 10 kinds of materials is shown in Fig. 1.
Blank sample in the present invention is a kind of substrate Zelkova schneideriana Hand.-Mazz. totally and without test substance.With blank sample as substrate, pass through
Mark-on experiment obtains detection limit, quantitative limit and the range of linearity of each material.Chromatograph and the mass spectrometry parameters of each material are shown in Table 1.
CAS, chromatographic retention, the range of linearity and the mass spectrometry parameters of table 1 test substance
* parent ion > quota ion (collision energy, eV).
2, the determination of wood sample sampling mode
Choose the square build Zelkova schneideriana Hand.-Mazz. blank sample that 3 length of sides are 3cm, be placed in 500mL beaker, add 100mg/L's
Complete mixed standard solution 50mL, adds appropriate simulation saliva and mixes, (can be suitable tiny heavy by whole for wood sample submergences
Thing or support auxiliary), seal.3 samples take out after soaking 1h, 5h and 24h respectively, stand overnight and dry in fume hood.
For soaking the sample of 1h, use low speed cutting saw to be cut the most successively on 6 surfaces of sample and obtain 3 groups of wood chips, its
In 0～3mm layer be A sample；3～6mm layers are B sample；Internal residue timber is C sample.Soak 5h and 24h
Sample in like manner；According to the Determination of Gross set up, 9 obtained are treated that test sample carries out 10 kinds of wood preservation agent contents respectively
Mensuration, result is as shown in Figure 2.
From Figure 2 it can be seen that along with the growth of soak time, in sample, the content entirety of timber preservative shows a rising trend.Timber is prevented
Rotten agent is internally migrated by wood surface with saliva, and the content in A sample is all far longer than B and C, even if soaking 24h's
Under the conditions of, material also and non-fully permeates uniformly at wood internal.Pyrethrin content in A sample is 5 times of B+C
Above, polystream aldehydes matter then reaches more than 32 times.And in actual migration is tested, research is that timber preservative is changed and register permanent residence along with the head of the household when this person moves to a new locality
Move solution to be migrated to outside by wood internal, anti-pushing manipulation can determine whether that actual migration material out is mainly in 3mm top layer,
3mm migrates out to the antiseptic substance in the timber of inside center is more difficult with migrating solution.Therefore the sampling side of this migration experiment
Formula is defined as taking sample surfaces 3mm layer；For ease of making the positive criteria sample of known content, and carry out the spy of Transport
Rope, pulverizes through beveller after wood sample takes surface 3mm layer.
Described in step (2), wood sample takes specific sampling mode, so that migrating experimental design more have theoretical foundation, with
Time be more beneficial for the making of positive criteria sample.Counter push away experiment by design, timber preservative with migrate solvent by wood surface to
Under the conditions of its internal migration long period, in the 3mm of timber top layer, wood preservation agent content is far longer than inside, thus releases reality
When border occurs transfer behavior, the timber preservative in mainly timber top layer 3mm migrates out, therefore desirable top layer 3 during sampling
mm。
3, the impact of solution ph is migrated
In the test of timber preservative total amount, need to be at 0.1mol/L solution of potassium carbonate back warp acetic anhydride reagent for polystream aldehydes matter
Derivatization, and the medium migrating experiment migrates solvent, if migrating energy after experiment terminates for simulation saliva, simulated sweat or water etc.
By directly performing the derivatization in migrating solution, the most more convenient.Saliva, simulated sweat, carbonic acid is simulated respectively at 40mL
Carrying out mark-on in potassium solution, the pH value of regulation simulation saliva and perspiration, to 2～9, is subsequently adding acetic anhydride and performs the derivatization.With
The response rate of solution of potassium carbonate is 100% benchmark, obtains migrating under different pH the relative recovery of 10 kinds of materials in solution.By
Fig. 3 and Fig. 4 is visible, and the response rate of 10 kinds of materials is affected substantially by migrating solution ph, and polystream aldehydes matter is at acid bar
Under part, the response rate is the lowest, along with strengthening of alkalescence is more conducive to derivative reaction and obtains the higher response rate；Pyrethrin is in acid
Property and neutrallty condition under relatively stable, at higher ph values the response rate start be deteriorated.Consider, select migration experiment knot
The pH value migrating solution after bundle is adjusted to 6, all substances all be can guarantee that to the relatively satisfactory response rate.
Migrating described in step (2) after adding 1mL internal standard working solution in solution, pH value is set as 6 for whole experiment
Result has decisive role.Owing to the character of polystream phenols and chrysanthemum esters timber preservative material differs widely, use gas phase
Chromatographic determination polystream aldehydes matter needs first to carry out acetic anhydride derivatization in solution of potassium carbonate medium.And complete in migration test
After, the medium of derivatization, is determined by the response rate by carefully optimizing for simulation saliva, simulated sweat or water, this research method
For the derivatization pH value that 10 kinds of timber preservatives are optimal, research finding, the variation of this value is studied for whole Transport
Result has a significant impact.
4, Transport and maximum mobility are drawn by experimental simulation
For polystream aldehydes matter, prepare 5mg/kg and 10mg/kg positive, prepared by 50mg/kg for pyrethrin
With 100mg/kg positive, migrating 1～10h respectively in simulation saliva and perspiration, bath temperature is set to 37 DEG C (normally
Human body temperature under the conditions of use), separately sampled mensuration each material migration amount under the conditions of simulation experiment, result is summarized in Fig. 5.
It should be noted that the detected level of decis is less than its quantitative limit, but still conversed migration amount by linear equation, be intended for ginseng
Examine.
Data in Fig. 5 are analyzed, show that 10 kinds of materials mainly have a following Transport:
(1) migrating in the 10h time, each substance rule out also differs.With the growth of migration time, many in sample
The migration amount entirety of chlorobenzene aldehydes matter shows a rising trend, such as 2,4-chlorophenesic acid, the positive sample of 5mg/kg and 10mg/kg
Product migration amount in saliva and perspiration increases the most in time and increases.And the migration amount of pyrethrin increases in time in sample
Basic in steady statue, such as cyfloxylate.This be likely due to pyrethrin within a short period of time i.e. timber body with move
Move and medium reaches balance.
(2) the migration amount that the timber preservative that content is identical migration amount in perspiration is substantially higher in saliva.Such as 2,3,4,6-
Tetrachlorophenol, 5mg/kg positive average mobility amount in perspiration is higher 9.1 times than in saliva, and 10mg/kg positive is then
High 8.6 times.But for different material, this species diversity is not quite identical, the 5mg/kg positive of such as gamma hch is at perspiration
Middle migration amount is almost equal with in saliva, and 10mg/kg positive migration amount in perspiration is slightly above saliva.
(3) for polystream aldehydes matter, in identical migration medium, the high sample migration amount of wood preservation agent content apparently higher than
The sample that content is low.Such as pentachlorophenol, 10mg/kg positive average mobility amount in perspiration is higher than 5mg/kg positive
2.9 times, in saliva, gap is 2.5 times.Pyrethrin rule in perspiration is identical with polystream aldehydes matter, and saliva
In liquid, migration amount is affected the most fairly obvious by content of material in sample.
By 10 kinds of actual total contents of material in above-mentioned all positive criteria samples are measured, with all of migration numerical quantity with
Corresponding total numerical quantity makees ratio, draws each material mobility in 10h.The most each material is the maximum of mobility in 10h
It is listed in table 2 and table 3.
From data in table, the pyrethrin maximum mobility in 10h is nearly all less than 1%, 100mg/kg positive sample
In product, decis mobility in saliva is minimum, and only 0.1%.The mobility of polystream aldehydes matter is the most much higher,
All more than 3%, individual other as in 10mg/kg sample 2,4, the 6-trichlorophenol, 2,4,6,-Ts maximum mobility in perspiration even can reach
69%.The most significantly difference occurs, may be relevant with two class materials dissolubility in aqueous, polystream aldehydes matter one
As be slightly soluble in water, as in pentachlorophenol water, dissolubility is 14mg/L, in 2,4,6-trichlorophenol, 2,4,6,-T water, dissolubility is 0.8g/L, and chrysanthemum
Ester is all insoluble in water, as Permethrin dissolubility in water, less than 0.03mg/L, is practically insoluble in water under decis room temperature.
This also can corroborate each other with other experimental result obtained herein.In Fig. 2, timber preservative through saliva to wood sample
Internal penetration, in the B sample obtained and C sample, pyrethrin content will be apparently higher than polystream aldehydes matter.Chrysanthemum esters thing
Matter easily through saliva to wood internal permeate, do not allow the most on the contrary The book of Changes saliva to people's vivo migration,
Polystream aldehydes matter is then easier in saliva migrates to human body.In Fig. 5, polystream aldehydes matter is due to dissolubility in water
Preferably, with the growth of migration time, wood internal gradually migrate in solution, therefore show a rising trend.And pyrethrin
It is insoluble in water, increases migration amount in time and be also not remarkably increased, it may be possible within a short period of time is i.e. situated between with migrating at timber body
Matter reaches balance.
In table 2 positive polystream aldehydes matter initial content and at the maximum mobility migrated in medium
In table 3 positive pyrethrin initial content and at the maximum mobility migrated in medium
Embodiment described above is only to be described the preferred embodiment of the present invention, not carries out the scope of the present invention
Limiting, on the premise of designing spirit without departing from the present invention, technical scheme is made by those of ordinary skill in the art
Various deformation and improvement, all should fall in the protection domain that claims of the present invention determines.
Claims (7)
1. the research method of timber preservative Transport in Wood children articles for use, it is characterised in that: comprise the steps:
(1) contained the positive criteria sample of 10 kinds of timber preservatives by self-control, measure sample by gas chromatography tandem mass spectrometry method
The total content of every kind of preservative reality in product；
(2) the migration amount of every kind of preservative in positive is measured: cut wood sample top layer 3mm with low speed cutting machine thick
Degree, ground instrument is ground into less than 2mm wood flour, accurately weighs 2g sample and fills in test tube in 50mL tool, adds and migrate
Solvent 40mL, described migration solvent is simulation saliva, simulated sweat or water, 37 DEG C, water-bath under the conditions of 100r/min
Cross 200 μm rustless steel screens after vibration 1～10h, obtain migration solution；1mL internal standard work is added in described migration solution
Make solution, pH value is adjusted to 6, add 1mL acetic anhydride and perform the derivatization, operate about 1min and be placed on shaking table vibration 10
min；By the solution after derivatization by solid through the Oasis HLB of the activation of 5mL methanol, 5mL deionized water balance in advance
Phase extraction column, through 5mL deionized water drip washing, utilizes vacuum pump to be drained by water, finally with 10mL ethyl acetate eluting,
Collect the eluent appropriate anhydrous sodium sulfate of addition to be dried, after vortex 30s, use gas chromatography tandem mass spectrometry detection method to measure；
(3) for the handling characteristics of Wood children articles for use, by setting different experimental simulation conditions, based on to every in sample
Plant total content and the mensuration of migration amount of preservative, the result obtained collected and analyzes, drawing in Wood children articles for use
The maximum mobility of every kind of timber preservative and Transport；
Described method measures total content and the migration amount of 10 kinds of antiseptic substance in sample simultaneously, and by experimental simulation condition
Carrying out Transport research, described preservative is 2,4-chlorophenesic acid, 2,4,5-trichlorophenol, 2,4,6,-Ts, 2,4,6-trichlorophenol, 2,4,6,-Ts, 2,3,
4,6-tetrachlorophenol, gamma hch, pentachlorophenol, cypermethrin, cyfloxylate, Permethrin and decis.
The research method of timber preservative Transport in Wood children articles for use the most according to claim 1, its feature exists
In: step (3) specifically includes following steps: for polystream aldehydes matter, preparation 5mg/kg and 10mg/kg is positive
Standard sample, prepares 50mg/kg and 100mg/kg positive for pyrethrin, respectively at different migration solvents
Middle migration 1～10h, bath temperature is set to 37 DEG C, separately sampled mensuration each material migration amount under the conditions of simulation experiment,
Result collects mapping, is intuitively analyzed transfer behavior；By to 10 kinds of actual total contents of material in all positive
It is measured, is calculated the ratio migrating numerical quantity and corresponding total numerical quantity, the most each material mobility in 10h,
The most each material maximum of mobility in 10h is maximum mobility, each by comparing in the positive of different content
The material maximum mobility in difference migrates solvent, and compare with result before, finally show that 10 kinds of timber are prevented
The Transport of rotten agent.
The research method of timber preservative Transport in Wood children articles for use the most according to claim 2, its feature exists
In: also include the preparation of positive, comprise the steps: to be ground into less than 2mm blank wood sample beveller
Wood flour, weigh appropriate wood flour in tool plug round-bottomed flask, a conical flask add complete mixed standard solution, and adds methanol
Dilution, it is ensured that the solution after dilution can be by whole wood flour submergences in pouring round-bottomed flask into；Round-bottomed flask is placed in shaking table vibration 2h
After stand overnight, it is ensured that preservative fully infiltrates into wood internal, then 35 DEG C, 170hPa backspin steam, revolve steamed journey
Middle pressure is gradually transitions 170hPa by 300hPa, and by solvent slow evaporation near dry, the most dry sawdust sample is laid in
On big surface plate, until solvent volatilizees completely, i.e. obtain positive.
The research method of timber preservative Transport in Wood children articles for use the most according to claim 3, its feature exists
In: described internal standard working solution is prepared from by the following method: weigh 50mg 2,3,4-trichlorophenol, 2,4,6,-T in 100mL brown
In volumetric flask, with the ethanol that volume ratio is 9:1/glacial acetic acid solution constant volume, it is configured to the internal standard storing solution of 500mg/L, then
It is diluted to the internal standard working solution that concentration is 5mg/L.
The research method of timber preservative Transport in Wood children articles for use the most according to claim 4, its feature exists
In:
The preparation method of described simulation saliva is prepared from by the following method: weigh sodium chloride 4.5g, potassium chloride 0.3g respectively,
Sodium sulfate 0.3g, ammonium chloride 0.4g, 90% lactic acid 3.0g, carbamide 0.2g, be settled to 1000mL with deionized water after mixing,
pH≈3；
Described simulated sweat is prepared from by the following method: weigh sodium bicarbonate 4.2g, sodium chloride 0.5g, potassium carbonate respectively
0.2g, is settled to 1000mL, pH ≈ 8.8 with deionized water after mixing.
The research method of timber preservative Transport in Wood children articles for use the most according to claim 1, its feature exists
In: step (1) specifically includes following steps: by sample comminution to less than 2mm wood flour, accurately weighs 2g, uses methanol
Supersound extraction 2 times, each 20mL, extracts 15min, in filtration also merging filtrate to centrifuge tube, adds 1mL internal standard
Working solution, at 4 DEG C, centrifugal 5min under the conditions of 13000r/min, is transferred to chicken after 0.45 μm PTFE membrane filtration
In heart bottle, 35 DEG C, 170hpa backspin inspissation be reduced to 2mL, in concentrated solution, add 40mL 0.1mol/L solution of potassium carbonate, shake
Adding 1mL acetic anhydride after even to perform the derivatization, exits in vibration limit, limit, operates about 1min and is placed on shaking table vibration 10min,
By the solution after derivatization by advance through the activation of 5mL methanol, the Oasis HLB Solid-Phase Extraction of 5mL deionized water balance
Post, through 5mL deionized water drip washing, utilizes vacuum pump to be drained by water, and finally with 10mL ethyl acetate eluting, collection is washed
De-liquid adds appropriate anhydrous sodium sulfate and is dried, and uses gas chromatography tandem mass spectrometry detection method to measure after vortex 30s.
The research method of timber preservative Transport in Wood children articles for use the most according to claim 1, its feature exists
In: the chromatography-mass spectroscopy condition of described gas chromatography tandem mass spectrometry detection method is: Agilent HP-5MS chromatographic column, specification
For 30m × 0.25mm i.d., 0.25 μm；Injector temperature 280 DEG C；Flow rate of carrier gas is 1.0mL/min；Splitless injecting samples,
Sample size 2 μ L；Temperature programming: initial temperature 60 DEG C, rises to 200 DEG C with 20 DEG C/min, then with 10 DEG C/min liter
To 280 DEG C and keep 8min；Solvent delay 5min；Transmission line temperature 250 DEG C；Ion source temperature 180 DEG C；EI electricity
From mode, ionizing energy 70eV, MRM pattern measures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310721822.4A CN103728405B (en) | 2013-12-24 | 2013-12-24 | The research method of timber preservative Transport in a kind of Wood children articles for use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310721822.4A CN103728405B (en) | 2013-12-24 | 2013-12-24 | The research method of timber preservative Transport in a kind of Wood children articles for use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103728405A CN103728405A (en) | 2014-04-16 |
| CN103728405B true CN103728405B (en) | 2016-12-07 |
Family
ID=50452569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310721822.4A Expired - Fee Related CN103728405B (en) | 2013-12-24 | 2013-12-24 | The research method of timber preservative Transport in a kind of Wood children articles for use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103728405B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104198621B (en) * | 2014-09-26 | 2016-04-13 | 云南中烟工业有限责任公司 | A kind of Simultaneously test method of multiclass antiseptic Special migration in paper and paperboard |
| CN105467034A (en) * | 2015-12-14 | 2016-04-06 | 山东凯盛新材料有限公司 | Gas chromatography detection method for benzotrichloride |
| CN106645448B (en) * | 2016-09-28 | 2019-11-29 | 广州纤维产品检测研究院 | The method for separating and detecting of phenol compound in textile |
| CN107525913B (en) * | 2017-08-18 | 2020-02-07 | 张承军 | Detection device and detection method for migration of phosphate plasticizer from fabric to skin |
| CN109187782A (en) * | 2018-09-03 | 2019-01-11 | 必维申优质量技术服务江苏有限公司 | The novel detection method of chlorophenol in textile |
| CN110568104A (en) * | 2019-09-24 | 2019-12-13 | 杭州市质量技术监督检测院 | Method for simultaneously measuring migration volumes of various chlorinated phenols in wooden tableware |
| CN112285252A (en) * | 2020-10-30 | 2021-01-29 | 中国检验检疫科学研究院 | Chemical risk assessment method for wood preservative in wooden toy |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997034747A1 (en) * | 1996-03-15 | 1997-09-25 | Michael Risk | Wood preserving composition |
| KR100942314B1 (en) * | 2009-03-18 | 2010-02-17 | 대한민국 | Measurement method for purity of didecyl-dimethyl-ammonium chloride using hplc-ms |
| CN102269743A (en) * | 2011-06-16 | 2011-12-07 | 中国检验检疫科学研究院 | Pre-processing method and use of wooden toy sample |
| CN102565207A (en) * | 2010-12-28 | 2012-07-11 | 中国检验检疫科学研究院 | Measuring method for migration quantity of harmful organisms in toy |
-
2013
- 2013-12-24 CN CN201310721822.4A patent/CN103728405B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997034747A1 (en) * | 1996-03-15 | 1997-09-25 | Michael Risk | Wood preserving composition |
| KR100942314B1 (en) * | 2009-03-18 | 2010-02-17 | 대한민국 | Measurement method for purity of didecyl-dimethyl-ammonium chloride using hplc-ms |
| CN102565207A (en) * | 2010-12-28 | 2012-07-11 | 中国检验检疫科学研究院 | Measuring method for migration quantity of harmful organisms in toy |
| CN102269743A (en) * | 2011-06-16 | 2011-12-07 | 中国检验检疫科学研究院 | Pre-processing method and use of wooden toy sample |
Non-Patent Citations (4)
| Title |
|---|
| PVC 塑料中邻苯二甲酸酯类增塑剂在体液中的迁移行为研究;杨左军 等;《聚氯乙烯》;20060228(第2期);第23页首段，第24页1.4节，第25-26页2.5节，2.9节，第27页表6 * |
| Rapid determination ot nineteen chlorophenols in wood，paper，cardboard，fruits，and fruit juiices by gas chromatography/mass spectrometry;Diserens J. M.;《Journal of AOAC international》;20011231;第84卷(第3期);page 853-860 * |
| 气相色谱／质谱联用分析玩具材料中木材防腐剂;卫碧文 等;《环境化学》;20110630;第30卷(第6期);1210-1213页 * |
| 气相色谱-串联质谱法测定木制儿童用品中的10种木材防腐剂;吕庆 等;《质谱学报》;20131130;第34卷(第6期);第321页"摘要"，第322页左栏1-3段，第322-323页1.2-1.5节，第325页2.3节，第327页表2，表3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103728405A (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103728405B (en) | The research method of timber preservative Transport in a kind of Wood children articles for use | |
| CN103529155B (en) | The assay method of wood preservation agent content in a kind of Wood children articles for use | |
| CN107474300A (en) | Pyrethroid insecticides molecularly imprinted polymer and its preparation method and application | |
| CN105675780A (en) | Method for simultaneous detection of various antibiotic residues in vegetables | |
| CN103265666A (en) | Malathion molecularly imprinted polymer and synthetic method of malathion restricted access media-molecularly imprinted polymer | |
| CN106198832A (en) | A kind of quality of production control method of intensified loquet distillate | |
| CN104569195B (en) | A kind of method of flavonoids effective constituent content in toothpaste detected containing baikal skullcap root | |
| Soponar et al. | High-performance thin-layer chromatography and three-dimensional image analysis for the determination of rutin in pharmaceutical preparations | |
| Klosi et al. | Galantamine content in Leucojum aestivum populations grown in northwest Albania | |
| CN103822994A (en) | Method for measuring residual quantity of paraquat and diquat in food | |
| CN105974015A (en) | Method for determining dimethomorph and gibberellin residual quantity of vegetables and fruits | |
| CN101543545A (en) | Traditional Chinese medicine preparation for curing rhinitis and quality control method thereof | |
| CN104596968A (en) | Method for rapidly and quantitatively detecting omethoate residue | |
| CN103163271B (en) | Measuring method for residual amount of cnidium lactone in tobacco leaves | |
| CN102680589B (en) | The method of LC-MS/MS ginseng Pesticide Residues | |
| CN102507802B (en) | Extraction method for residual pyrethroid pesticides in water environment | |
| CN102435565A (en) | Quantitative measurement method for theanine | |
| CN104807727B (en) | The detection method of benzophenone compound the amount of migration in a kind of textile | |
| Garau et al. | Residue-free wines: fate of some quinone outside inhibitor (QoI) fungicides in the winemaking process | |
| CN106596442A (en) | Method for rapidly and quantitatively detecting phorate residue | |
| CN104459011A (en) | Detecting method for leucoderma treatment tablet containing eight traditional Chinese medicines | |
| CN103995080B (en) | The method for building up of a kind of Aconitum teucostomum and processed product HPLC finger-print thereof and finger-print thereof | |
| CN100363048C (en) | Quality control method for pile eliminating tablet | |
| CN105628843A (en) | Solid-phase membrane extraction-gas chromatography electron capture detection method for eight pyrethroid pesticides in water body | |
| CN103105439B (en) | Method for simultaneously determining residual organochlorine, pyrethroid and organophosphorus pesticides in food |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161207 Termination date: 20191224 |