CN107144499A - The research method of bisphenol-A Transport in simulated body fluid in ABS plastic toy - Google Patents
The research method of bisphenol-A Transport in simulated body fluid in ABS plastic toy Download PDFInfo
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Abstract
The invention discloses a kind of research method of bisphenol-A Transport in simulated body fluid in ABS plastic toy, including：Prepare simulated body fluid；Bisphenol-A standard reserving solution is prepared, is added in hybrid analog-digital simulation saliva and sweat, the rate of recovery is determined；Standard sample is added into simulated sweat or simulation saliva, water-bath vibration 10min~140h determines migration amount；With reference to Fick second laws, diffusion coefficient equation and equation for distribution coefficients, diffusion coefficient D and distribution coefficient K of the bisphenol-A in simulated body fluid in ABS plastic are obtainedP/F；Prediction the maximum migration amount of bisphenol-A and balances each other the time when balancing each other.The present invention studies Transport of the bisphenol-A in saliva and sweat in ABS plastic toy material with liquid chromatography tandem mass spectrometry, and set up migration models of the bisphenol-A in body fluid in a kind of effective plastic toy, reduction import and export the security risk of toy, improve toy import and export detectability, reduce toy inferior to the harm of the person and environment in terms of all tools be of great significance.
Description
Technical field
The present invention relates to the research field of bisphenol-A Transport in ABS plastic toy, more particularly in ABS plastic toy
The research method of bisphenol-A Transport in simulated body fluid.
Background technology
Bisphenol-A is widely used in plastic toy, feeding bottle, water bottle and other hundreds of days as good plastic additive
In the manufacturing process of articles for use.Bisphenol-A belongs to " environmental hormone ", in recent years, the developed countries and regions such as the U.S., Canada, European Union
Assert that bisphenol-A is toxic chemical substance successively, and bisphenol-A limit has been worked out one after another to articles for children, packaging for foodstuff, container for drink etc.
Amount standard, or even bisphenol-A is disabled completely to some articles for children.On November 14th, 2016, the meeting of the toy safety committee of European Union
In view, member state has voted through the adjustment motion that bisphenol-A is limited the quantity in the toy safety instruction that EU Committee is proposed, mainly
For the bisphenol-A in the toy for children of less than three years old, limitation is adjusted to 0.01mg/L from original 0.1mg/L.This European Union
Propose that bisphenol-A migration amount in toy is greatly reduced again, be upgrading again to the instruction of " in history most tight " toy, will be to China's toy
Cause significant impact in outlet.In plastic toy the migration amount of bisphenol-A by the surface area size of material, body fluid species, body fluid volume,
The influence of the factors such as transit time.Bisphenol-A has can be accumulative, with child getting in contact longer, youngster of containing the bisphenol-A plastic toy time
The bisphenol-A that child is accumulated in vivo is more, but the migration amount of bisphenol-A is to be reached with the increase of time of contact in plastic toy
To balance, migration amount now is exactly the gross migration of the bisphenol-A of this plastic toy.
But in the prior art, often needed by unlimited number of reality during the migration amount of bisphenol-A in detection plastic toy
Test, the time that consuming is not waited for tens to hundreds of hours can just detect, time and effort consuming, the detectability for importing and exporting toy is low
Under.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art there is provided a kind of detection efficiency is high, time saving province
The research method of bisphenol-A Transport in simulated body fluid in power and the high ABS plastic toy of accuracy rate.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
The research method of bisphenol-A Transport in simulated body fluid, comprises the following steps in a kind of ABS plastic toy：
(1) simulated body fluid is prepared：Including preparing Simulated sweat and saliva；
(2) bisphenol-A standard reserving solution is prepared, and bisphenol-A standard reserving solution is diluted to various concentrations step by step with methanol
Storing solution, is added separately in hybrid analog-digital simulation saliva and sweat, is determined after extract solution is purified according to SPE condition with methanol
Hold, the rate of recovery of bisphenol-A is determined using liquid chromatography-tandem mass spectrometry side, and set up standard recovery working curve；
(3) prepare bisphenol-A standard sample in ABS plastic, standard sample is put into sample bottle with cover, and add the mould
Intend sweat or simulation saliva, in being vibrated under 37 ± 2 DEG C of water-baths, transit time 10min~140h will be carried according to SPE condition
Take liquid to use methanol constant volume after purifying, the migration amount of bisphenol-A is determined using liquid chromatography-tandem mass；
(4) Fick second laws, diffusion coefficient equation and equation for distribution coefficients, the experiment mould different by setting are combined
Plan condition, the migration amount measured based on step (3) obtains Transport mould of the bisphenol-A in simulated body fluid in ABS plastic
Type：Diffusion coefficient D and distribution coefficient KP/F；
(5) diffusion coefficient D and distribution coefficient K obtained by step (4)P/F, in the case of the total content of known bisphenol-A,
The Transport of bisphenol-A when balancing each other can be predicted：Maximum migration amount and balance each other the time.
It is used as the further improvement of above-mentioned technical proposal：
It is preferred that, the specific analytical method of the step (4) is：
(41) transition process of thing, i.e. equation (1) are migrated with the partial differential equation description of Fick second laws：
In formula：C is the migration amount for migrating thing in time t and position x；D is to migrate the diffusion coefficient of thing in the polymer, single
Position is cm2/s；
(42) migration of migration thing in polymer is described with the solution and diffusion coefficient equation (2) of equation (1)：
In formula：MF,tThe migration amount that thing enters simulated solution is migrated for t, unit is mg；MF,LFor in whole transition process
The migration amount that thing enters simulated solution is migrated, unit is mg；LpFor the thickness of polymer, unit is cm；
For short time migration, ierfc [nLP/(Dt)0.5] → 0, i.e. simulated solution initial time are without migration thing, MF,L=
MP,0, MP,0To migrate the initial content of thing in polymer, so equation (2) is reduced to below equation (3), diffusion coefficient D is calculated：
(43) migration thing is obtained in the polymer distribution coefficient K alternate with simulated solution two by equation for distribution coefficients (4)P/F：
In formula：MF,∞Migration amount during to reach migration balance in simulated solution；Vp is the polymeric material of contact simulated solution
Volume, unit is cm3；VFFor the volume of simulated solution, unit is cm3。
It is preferred that, diffusion coefficient D of the bisphenol-A in 37 DEG C of Imitating salivas and simulated sweat in the ABS plastic toy
Respectively 4.6414 × 10-13cm2s-1With 1.9319 × 10-13cm2s-1；Distribution coefficient KP/FRespectively 10877.4 and 16229.8.
It is preferred that, maximum migration amount of the bisphenol-A in simulation saliva and simulated sweat is respectively 3.28mg in the ABS
kg-1And 2.18mgkg-1。
It is preferred that, in the step (2), the standard recovery working curve is：Y=22608.3x+58.6239 is related
Coefficient is 0.9995.
It is preferred that, bisphenol-A standard sample is diameter 14.6mm sheet in the ABS plastic, by bisphenol A compounds, is resisted
Oxidant, antistatic additive, diffusant are made after being mixed with acrylonitrile-butadiene-styrene copolymer through melting extrusion and section；
The step (3) is specially：Bisphenol-A standard sample in diameter 14.6mm sheet ABS plastic is taken, three are portion, use metal
Silk is stringed together, and bead interval is used between every, and sample string is made, and is put into 50mL samples with cover in the bending lopping of wire low side
In product bottle, the simulated sweat described in 20mL or simulation saliva, methanol constant volume 10mL are added.
It is preferred that, the SPE condition is：From OROCHEM c18 posts, Supelclean LC-18 posts, CNW
Bond Coconut charcoal posts, Cleanert PA-SPE posts, Bond Elut-Certify posts, Oasis HLB posts,
SPE-PAK tc18 posts or Chromab columns easy posts are solid-phase extraction column；From acetonitrile, ethyl acetate, n-hexane,
Dichloromethane or methanol are extractant；Extractant volume is 2mL-15mL.
It is preferred that, in the liquid chromatography-tandem mass, chromatographic condition is：Waters XBridge C18Color
Post is composed, specification is 2.1mm × 150mm, i.d.3.5 μm；Mobile phase：A is 0.1% ammoniacal liquor, and B is methanol；Isocratic elution：0~
2min, A are that 10%, B is 90%；Flow is 0.30mLmin-1；Column temperature is 30 DEG C；Sample size is 5 μ L；
Mass Spectrometry Conditions are：Negative electrospray ionization source；Capillary voltage is 2.5KV；Radio-frequency lens voltage is 0.5V；Ion gun
150 DEG C of temperature；500 DEG C of solvent temperature degree is removed, solvent stream amount 500Lh is removed-1；Taper hole throughput 50Lh-1；Collision gas
It is not less than 99.999% argon gas for purity, collision air pressure is 3.2 × 10-4kPa；Data acquisition scheme：Multiple-reaction monitoring；Bis-phenol
A mass spectrometry parameters are：Retention time 1.30min；Monitor ion pair m/z (227.1/212.1) taper hole voltage 30V, impact energy
Measure 25eV；Monitor ion pair m/z (227.1/133.1) taper hole voltage 30V, collision energy 28eV.
It is preferred that, the compound method of the simulated sweat is：Sodium chloride 5.0g, urea 1.0g, lactic acid 1.0g are weighed, with suitable
Measure after deionized water dissolving, constant volume 1L, adjust pH value to be 6.5 ± 0.1 with 1% ammoniacal liquor；
It is described simulation saliva compound method be：Weigh Magnesium dichloride hexahydrate 0.17g, CALCIUM CHLORIDE DIHYDRATE 0.15g, three water
Potassium phosphate,monobasic 0.76g, potassium carbonate 0.53g, sodium chloride 0.33g, potassium chloride 0.75g are closed, it is fixed after being dissolved with appropriate amount of deionized water
Hold 1L, adjust pH value to be 6.8 ± 0.1 with 1% hydrochloric acid.
It is preferred that, the compound method of the bisphenol-A standard reserving solution：Weigh the bisphenol-A that appropriate purity is not less than 98.5%
Standard substance, is accurate to 0.1mg, and it is 1000mgL that mass concentration is configured to methanol-1Single Standard Stock solutions.
Compared with prior art, the advantage of the invention is that：
The present invention selects the ABS plastic sample for containing bisphenol-A as research object, with Liquid Chromatography-Tandem Mass Spectrometry pair
Transport of the incretion interferent bisphenol-A in saliva and sweat is studied in ABS plastic toy material, establishes one kind
The research method of Transport of the bisphenol-A in body fluid in effective plastic toy, obtains the migration models (diffusion of bisphenol-A
Coefficient and distribution coefficient), as long as in the case of the total content of known bisphenol-A, can be predicted by distribution coefficient and diffusion coefficient
The maximum migration amount of bisphenol-A, with detection efficiency is high, time saving and energy saving and high accuracy for examination, toy is imported and exported for reduction
Security risk and raising toy import and export detectability and provide technical support, to reducing toy inferior to personal and environment
All tool is of great significance in terms of harm.
Brief description of the drawings
Fig. 1 is SPE condition optimization figure.
Fig. 2 be in different simulated solutions bisphenol-A with time migrating data figure.
Fig. 3 is M in simulation salivaF,t/Mp,0With t0.5Ratio.
Fig. 4 is M in simulated sweatF,t/Mp,0With t0.5Ratio.
Embodiment
For the ease of understanding the present invention, more complete is made to the present invention below in conjunction with Figure of description and preferred embodiment
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Embodiment：
The research method of bisphenol-A Transport in simulated body fluid, comprises the following steps in a kind of ABS plastic toy：
(1) simulated body fluid is prepared：Including preparing Simulated sweat and saliva；
(2) bisphenol-A standard reserving solution is prepared, and bisphenol-A standard reserving solution is diluted to various concentrations step by step with methanol
Storing solution, is added separately in hybrid analog-digital simulation saliva and sweat, is determined after extract solution is purified according to SPE condition with methanol
Hold, the rate of recovery of bisphenol-A is determined using liquid chromatography-tandem mass spectrometry side, and set up standard recovery working curve；
(3) prepare bisphenol-A standard sample in ABS plastic, standard sample is put into sample bottle with cover, and add the mould
Intend sweat or simulation saliva, in being vibrated under 37 ± 2 DEG C of water-baths, transit time 10min~140h will be carried according to SPE condition
Take liquid to use methanol constant volume after purifying, the migration amount of bisphenol-A is determined using liquid chromatography-tandem mass；
(4) Fick second laws, diffusion coefficient equation and equation for distribution coefficients, the experiment mould different by setting are combined
Plan condition, the migration amount measured based on step (3) obtains Transport mould of the bisphenol-A in simulated body fluid in ABS plastic
Type：Diffusion coefficient D and distribution coefficient KP/F；
(5) diffusion coefficient D and distribution coefficient K obtained by step (4)P/F, in the case of the total content of known bisphenol-A,
The Transport of bisphenol-A when balancing each other can be predicted：Maximum migration amount and balance each other the time.
Specific experiment analysis process is as follows：
1 preliminary preparation
1.1 instruments and reagent
The type high performance liquid chromatographs of U.S. Waters Alliance 2695；U.S. Waters Quattro micro API
Type mass spectrograph；U.S.'s Millipore Milli-Q type Superpure water machines；Switzerland's BUCHI R-3 type Rotary Evaporators.
Bisphenol-A standard reserving solution：Appropriate bisphenol-A (purity is not less than 98.5%) standard substance (being accurate to 0.1mg) is weighed,
It is 1000mgL that mass concentration is configured to methanol-1Single Standard Stock solutions.
Bisphenol-A standard sample in ABS plastic：Detection Science and Technology Ltd. is really marked by Dongguan City to customize and purchase (a diameter of
14.6mm sheet, by bisphenol A compounds, antioxidant, antistatic additive, diffusant and acrylonitrile-butadiene-styrene (ABS) copolymerization
Formed after thing mixing through melting extrusion and the system of cutting into slices).
Methanol, dichloromethane, acetonitrile, tetrahydrofuran, ethyl acetate, n-hexane, absolute ethyl alcohol are chromatographically pure, Qi Tashi
Agent is pure to analyze.
1.2 instrument conditions of work
1.2.1 liquid phase chromatogram condition
U.S. Waters XBridge C18Chromatographic column (2.1mm × 150mm, 3.5 μm)；Mobile phase：A is 0.1% ammoniacal liquor, B
For methanol；Isocratic elution：0~2min, A are that 10%, B is 90%.Flow is 0.30mLmin-1；Column temperature is 30；DEG C sample size
For 5 μ L.
1.2.2 Mass Spectrometry Conditions
Negative electrospray ionization source (ESI-)；Capillary voltage is 2.5KV；Radio-frequency lens voltage is 0.5V；Ion source temperature
150；DEG C solvent temperature degree 500 is removed, DEG C remove solvent stream amount 500Lh-1；Taper hole throughput 50Lh-1；Collision gas are argon
Gas (purity is not less than 99.999%), collision air pressure is 3.2 × 10-4kPa；Data acquisition scheme：Multiple-reaction monitoring；Bisphenol-A
Mass spectrometry parameters are：Retention time 1.30min；Monitor ion pair m/z (227.1/212.1) taper hole voltage 30V, collision energy
25eV；Monitor ion pair m/z (227.1/133.1) taper hole voltage 30V, collision energy 28eV.
2 experimental methods
2.1 Simulated sweat and salivas are prepared
Simulated sweat：Sodium chloride 5.0g, urea 1.0g, lactic acid 1.0g accurately are weighed, it is fixed after being dissolved with appropriate amount of deionized water
Hold 1L, adjust pH value to be 6.5 ± 0.1 with 1% ammoniacal liquor.
Simulate saliva：Accurately weigh Magnesium dichloride hexahydrate 0.17g, CALCIUM CHLORIDE DIHYDRATE 0.15g, the hydrogen potassium of three hypophosphite monohydrate one
0.76g, potassium carbonate 0.53g, sodium chloride 0.33g, potassium chloride 0.75g, after being dissolved with appropriate amount of deionized water, constant volume 1L uses 1% salt
Acid adjusts pH value to be 6.8 ± 0.1.
2.2 determine bisphenol-A migration amount
Bisphenol-A standard sample in a diameter of 14.6mm ABS plastic is taken, three are portion.With wire by sample strip string
Get up to be formed and bead interval is used between sample string, every, the bending lopping of wire low side；The sample string prepared is put into
In 50mL sample bottles with cover, it is ensured that sample strip is not contacted with sample bottle bottom.20mL simulated solutions (saliva or sweat) are added, are covered
Lid, 10min~140h is shaken under (37 ± 2) DEG C water-bath, extract solution is purified according to SPE condition, uses methanol constant volume
10mL, is determined using liquid chromatography-tandem mass spectrometry side.
2.3 set up standard recovery working curve：According to test method, bisphenol-A standard reserving solution methanol is diluted step by step
Into 0.1mgL-1, 0.2mgL-1, 0.5mgL-1, 1.0mgL-1, 2.0mgL-1, 5.0mgL-1, 1mL is then respectively taken,
It is added in hybrid analog-digital simulation saliva and sweat, purifies extract solution according to SPE condition, methanol constant volume 10mL is used, using liquid
Phase chromatogram-tandem mass spectrum side determines the rate of recovery of bisphenol-A, obtains 0.01mgL-1, 0.02mgL-1, 0.05mgL-1,
0.1mg·L-1, 0.2mgL-1, 0.5mgL-1Standard recovery working curve y=22608.3x+58.6239, coefficient correlation
For 0.9995.Simulation saliva and sweat belong to high salt split system, can produce matrix effect, influence test result, set up standard and return
It is that the matrix effect of whole experiment process is disturbed in order to eliminate simulation saliva and sweat to receive working curve.
2.4 choose SPE condition
As shown in figure 1, three of SPE condition it is main investigate factor for the optimization of solid phase column, the optimization of extractant,
Extract the optimization of volume.So, in the case where two conditions are constant, investigate another condition.Conventional solid phase column is randomly selected,
Model SPE-PAK tc18, with methanol as extractant, according to test method, investigate 2mL, 5mL, 10mL, 15mL, 20mL different
The rate of recovery of the bisphenol-A under volume is extracted, when using more than 5mL extractants, the rate of recovery tends to balance, so extractant is used
10mL is advisable.Choose 8 kinds of conventional solid-phase extraction columns, OROCHEM c18 posts, Supelclean LC-18 posts, CNW bond
Coconut charcoal posts, Cleanert PA-SPE posts, Bond Elut-Certify posts, Oasis HLB posts, SPE-PAK
Tc18 posts, Chromab columns easy posts.Using methanol as extractant, extractant volume is 10mL, according to test method,
The rate of recovery of the bisphenol-A under different solid phase columns is investigated, when carrying out SPE using SPE-PAK tc18 posts, recovering effect is most
It is good, so this experiment is used as solid-phase extraction column using SPE-PAK tc18 posts.Choose conventional acetonitrile, ethyl acetate, n-hexane, two
Chloromethanes, five kinds of extractants of methanol, using SPE-PAK tc18 posts as solid phase column extraction column, extractant volume is 10mL, according to
Test method, investigates the rate of recovery of the bisphenol-A under different extractants, when methanol is as extractant, recovering effect is best.
The precision of 2.5 methods
According to 2.2 section methods, 1h, 2h, 3h simulation saliva and sweat extract solution is taken to be measured, it is parallel to do 6 parts of samples, meter
The precision RSD of calculation method is 3.66%-4.34%, is shown in Table 1.
The precision of the method for table 1
The research of 2.6 Transports
2.6.1 migration models
As a rule, compound migration such as diffusion process, it then follows Fick diffusion laws.Existing frequently-used Fick second determines
The partial differential equation of rule describe the transition process of compound, i.e. formula (1)：
In formula：C is migration amount of the compound in time t (s) He position x (cm)；D is the diffusion of compound in the polymer
Coefficient (cm2/s)。
For the description of transition process, following primary condition is assumed initially that：
1) initial time, migration thing is uniformly distributed in the polymer, and any migration thing is free of in analogies；2) thing is migrated
Only enter analogies from the side of polymer；3) migration thing does not have concentration gradient in analogies；4) surface mass transfer coefficient is long-range
In diffusion coefficient, illustrate that the transition process in polymer meets Fick dispersal behaviors；5) diffusion coefficient D in transition process and point
Distribution coefficient KP,FFor constant；6) boundary effect between polymer and analogies and interaction are ignored.
The transition process of compound can represent the migration under different hypothesis, initial, boundary condition with the solution of equation (1)
Process.
The migration of compound commonly uses the solution and equation (2) of equation (1) to describe in polymer：
In formula：MF,t(mg) the migration amount that thing enters analogies is migrated for t；MF,L(mg) be whole transition process in move
Move the migration amount that thing enters simulated solution；Lp(cm) it is the thickness of polymer.
For short time migration, ierfc [nLP/(Dt)0.5] → 0, i.e. analogies initial time are without migration thing, MF, L=
MP,0, MP,0To migrate the initial content of thing in polymer, so equation (2) can be reduced to：
Transition process from polymer to analogies is main by kinetic factor diffusion coefficient (D) and Thermodynamics distribution
Coefficient (KP/F) determine.Diffusion coefficient is to weigh migration thing in the alternate spread condition of the analogies two of polymer, and distribution coefficient is determined
Distribution condition of the thing in two-phase is migrated during fixed migration balance.Diffusion coefficient (D) can be obtained by equation (3), distribution coefficient (KP/F)
It can be obtained by equation (4).
In formula：Vp is the volume of the polymeric material of contact analogies, unit cm3；VFFor the volume of analogies, unit
cm3。
2.6.2ABS in plastic toy bisphenol-A in simulated body fluid migration models (including diffusion coefficient D and distribution be
Number KP/F) foundation
It was found from above-mentioned migration models, the transition process from polymer to analogies is main by diffusion coefficient (D) and distribution
Coefficient (KP/F) determine.The diffusion coefficient D of transition process can use M according to equation (3)F,t/MP,0With t1/2Slope try to achieve, such as Fig. 3
It is respectively 4.6414 × 10 with diffusion coefficient D of the bisphenol-A in simulation saliva and simulated sweat shown in Fig. 4, is tried to achieve-13(cm2s-1)
With 1.9319 × 10-13(cm2s-1).Equally, the distribution coefficient (K of transition processP/F) can be tried to achieve according to equation (4), bisphenol-A can be obtained
Distribution coefficient K in simulation saliva and simulated sweatP/FRespectively 10877.4 and 16229.8.
2.6.3 migrating data of the bisphenol-A in simulated body fluid is determined
The total amount of bisphenol-A is 1282mgkg in bisphenol-A standard sample in ABS plastic-1.Mesh is determined according to 2.2 section methods
The migration amount of standard specimen product, as shown in Figure 2.As can be seen from Figure 2, bisphenol-A migration changes of contents in saliva and simulated sweat is simulated to become
Gesture is consistent, all gradually increases with the extension migration amount of transit time, chemical balance is finally reached in 120h.Due to sweat and
The composition of saliva is different with pH, causes to migrate content difference.Pass through distribution coefficient of the bisphenol-A in simulation saliva and simulated sweat
KP/FRespectively 10877.4 and 16229.8, the maximum migration amount of bisphenol-A in simulation saliva and simulated sweat that can estimate is respectively
3.28mg·kg-1And 2.18mgkg-1。
To sum up, according to Fick diffusion laws and obtained diffusion coefficient D and distribution coefficient KP/F, bis-phenol in ABS plastic toy
A can be set up at 37 DEG C through simulating the migration models of saliva and simulated sweat, further according to bisphenol-A in migration models and toy
The Transport and its maximum migration amount of bisphenol-A just can be predicted in total amount.Migration experiment need not be done one by one, so that by theory and practice
Combine well, reach the purpose saved time and cost.
Claims (10)
1. the research method of bisphenol-A Transport in simulated body fluid in a kind of ABS plastic toy, it is characterised in that：Including
Following steps：
(1) simulated body fluid is prepared：Including preparing Simulated sweat and saliva；
(2) bisphenol-A standard reserving solution is prepared, and bisphenol-A standard reserving solution is diluted to the deposit of various concentrations step by step with methanol
Liquid, is added separately in hybrid analog-digital simulation saliva and sweat, and methanol constant volume is used after extract solution is purified according to SPE condition, is adopted
The rate of recovery of bisphenol-A is determined with liquid chromatography-tandem mass spectrometry side, and sets up standard recovery working curve；
(3) prepare bisphenol-A standard sample in ABS plastic, standard sample is put into sample bottle with cover, and add the simulation sweat
Liquid or simulation saliva, in being vibrated under 37 ± 2 DEG C of water-baths, transit time 10min~140h, according to SPE condition by extract solution
Methanol constant volume is used after purification, the migration amount of bisphenol-A is determined using liquid chromatography-tandem mass；
(4) Fick second laws, diffusion coefficient equation and equation for distribution coefficients, the experimental simulation bar different by setting are combined
Part, the migration amount measured based on step (3) obtains Transport model of the bisphenol-A in simulated body fluid in ABS plastic：Expand
Dissipate coefficient D and distribution coefficient KP/F；
(5) diffusion coefficient D and distribution coefficient K obtained by step (4)P/F, can in the case of the total content of known bisphenol-A
Predict the Transport of bisphenol-A when balancing each other：Maximum migration amount and balance each other the time.
2. research method according to claim 1, it is characterised in that：The specific analytical method of the step (4) is：
(41) transition process of thing, i.e. equation (1) are migrated with the partial differential equation description of Fick second laws：
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<mrow>
<mo>&part;</mo>
<msup>
<mi>x</mi>
<mn>2</mn>
</msup>
</mrow>
</mfrac>
<mo>-</mo>
<mo>-</mo>
<mo>-</mo>
<mrow>
<mo>(</mo>
<mn>1</mn>
<mo>)</mo>
</mrow>
</mrow>
In formula：C is the migration amount for migrating thing in time t and position x；D is to migrate the diffusion coefficient of thing in the polymer, and unit is
cm2/s；
(42) migration of migration thing in polymer is described with the solution and diffusion coefficient equation (2) of equation (1)：
<mrow>
<mfrac>
<msub>
<mi>M</mi>
<mrow>
<mi>F</mi>
<mo>,</mo>
<mi>t</mi>
</mrow>
</msub>
<msub>
<mi>M</mi>
<mrow>
<mi>F</mi>
<mo>,</mo>
<mi>L</mi>
</mrow>
</msub>
</mfrac>
<mo>=</mo>
<mn>2</mn>
<msup>
<mrow>
<mo>(</mo>
<mfrac>
<mrow>
<mi>D</mi>
<mi>t</mi>
</mrow>
<msubsup>
<mi>L</mi>
<mi>P</mi>
<mn>2</mn>
</msubsup>
</mfrac>
<mo>)</mo>
</mrow>
<mn>0.5</mn>
</msup>
<mo>{</mo>
<mfrac>
<mn>1</mn>
<msup>
<mi>&pi;</mi>
<mn>0.5</mn>
</msup>
</mfrac>
<mo>+</mo>
<mn>2</mn>
<munderover>
<mo>&Sigma;</mo>
<mrow>
<mi>n</mi>
<mo>=</mo>
<mn>1</mn>
</mrow>
<mi>&infin;</mi>
</munderover>
<mrow>
<mo>(</mo>
<mo>-</mo>
<mn>1</mn>
<mo>)</mo>
</mrow>
<mi>i</mi>
<mi>e</mi>
<mi>r</mi>
<mi>f</mi>
<mi>c</mi>
<mo>&lsqb;</mo>
<mfrac>
<mrow>
<msub>
<mi>nL</mi>
<mi>P</mi>
</msub>
</mrow>
<msup>
<mrow>
<mo>(</mo>
<mi>D</mi>
<mi>t</mi>
<mo>)</mo>
</mrow>
<mn>0.5</mn>
</msup>
</mfrac>
<mo>&rsqb;</mo>
<mo>}</mo>
<mo>-</mo>
<mo>-</mo>
<mo>-</mo>
<mrow>
<mo>(</mo>
<mn>2</mn>
<mo>)</mo>
</mrow>
</mrow>
In formula：MF,tThe migration amount that thing enters simulated solution is migrated for t, unit is mg；MF,LTo be migrated in whole transition process
Thing enters the migration amount of simulated solution, and unit is mg；LpFor the thickness of polymer, unit is cm；
For short time migration, ierfc [nLP/(Dt)0.5] → 0, i.e. simulated solution initial time are without migration thing, MF,L=MP,0,
MP,0To migrate the initial content of thing in polymer, so equation (2) is reduced to below equation (3), diffusion coefficient D is calculated：
<mrow>
<mfrac>
<msub>
<mi>M</mi>
<mrow>
<mi>F</mi>
<mo>,</mo>
<mi>t</mi>
</mrow>
</msub>
<msub>
<mi>M</mi>
<mrow>
<mi>P</mi>
<mo>,</mo>
<mn>0</mn>
</mrow>
</msub>
</mfrac>
<mo>=</mo>
<mfrac>
<mn>2</mn>
<msub>
<mi>L</mi>
<mi>P</mi>
</msub>
</mfrac>
<msup>
<mrow>
<mo>(</mo>
<mfrac>
<mrow>
<mi>D</mi>
<mi>t</mi>
</mrow>
<mi>&pi;</mi>
</mfrac>
<mo>)</mo>
</mrow>
<mn>0.5</mn>
</msup>
<mo>-</mo>
<mo>-</mo>
<mo>-</mo>
<mrow>
<mo>(</mo>
<mn>3</mn>
<mo>)</mo>
</mrow>
</mrow>
(43) migration thing is obtained in the polymer distribution coefficient K alternate with simulated solution two by equation for distribution coefficients (4)P/F：
<mrow>
<msub>
<mi>K</mi>
<mrow>
<mi>P</mi>
<mo>/</mo>
<mi>F</mi>
</mrow>
</msub>
<mo>=</mo>
<mfrac>
<msub>
<mi>C</mi>
<mrow>
<mi>P</mi>
<mo>,</mo>
<mi>&infin;</mi>
</mrow>
</msub>
<msub>
<mi>C</mi>
<mrow>
<mi>F</mi>
<mo>,</mo>
<mi>&infin;</mi>
</mrow>
</msub>
</mfrac>
<mo>=</mo>
<mfrac>
<mrow>
<msub>
<mi>M</mi>
<mrow>
<mi>P</mi>
<mo>,</mo>
<mn>0</mn>
</mrow>
</msub>
<mo>-</mo>
<msub>
<mi>M</mi>
<mrow>
<mi>F</mi>
<mo>,</mo>
<mi>&infin;</mi>
</mrow>
</msub>
</mrow>
<msub>
<mi>M</mi>
<mrow>
<mi>F</mi>
<mo>,</mo>
<mi>&infin;</mi>
</mrow>
</msub>
</mfrac>
<mo>&times;</mo>
<mfrac>
<msub>
<mi>V</mi>
<mi>F</mi>
</msub>
<msub>
<mi>V</mi>
<mi>P</mi>
</msub>
</mfrac>
<mo>-</mo>
<mo>-</mo>
<mo>-</mo>
<mrow>
<mo>(</mo>
<mn>4</mn>
<mo>)</mo>
</mrow>
</mrow>
In formula：MF,∞Migration amount during to reach migration balance in simulated solution；Vp is the body of the polymeric material of contact simulated solution
Product, unit is cm3；VFFor the volume of simulated solution, unit is cm3。
3. research method according to claim 2, it is characterised in that：Bisphenol-A mould at 37 DEG C in the ABS plastic toy
The diffusion coefficient D intended in saliva and simulated sweat is respectively 4.6414 × 10-13cm2s-1With 1.9319 × 10-13cm2s-1；Distribution
COEFFICIENT KP/FRespectively 10877.4 and 16229.8.
4. research method according to claim 1, it is characterised in that：Bisphenol-A is in simulation saliva and simulation sweat in the ABS
Maximum migration amount in liquid is respectively 3.28mgkg-1And 2.18mgkg-1。
5. research method according to claim 1, it is characterised in that：In the step (2), the standard recovery work is bent
Line is：Y=22608.3x+58.6239, coefficient correlation is 0.9995.
6. research method according to claim 1, it is characterised in that：Bisphenol-A standard sample is diameter in the ABS plastic
14.6mm sheet, by bisphenol A compounds, antioxidant, antistatic additive, diffusant and acrylonitrile-butadiene-styrene (ABS) copolymerization
It is made after thing mixing through melting extrusion and section；The step (3) is specially：Take double in diameter 14.6mm sheet ABS plastic
Phenol A standard samples, three are portion, stringed together with wire, bead interval is used between every, wire low side is bent to
Circle, is made sample string, and is put into 50mL sample bottles with cover, adds the simulated sweat described in 20mL or simulation saliva, and methanol is fixed
Hold 10mL.
7. research method according to claim 1, it is characterised in that：The SPE condition is：From OROCHEM
C18 posts, Supelclean LC-18 posts, CNW bond Coconut charcoal posts, Cleanert PA-SPE posts, Bond
Elut-Certify posts, Oasis HLB posts, SPE-PAK tc18 posts or Chromab columns easy posts are SPE
Post；It is extractant from acetonitrile, ethyl acetate, n-hexane, dichloromethane or methanol；Extractant volume is 2mL-15mL.
8. research method according to claim 1, it is characterised in that：In the liquid chromatography-tandem mass,
Chromatographic condition is：Waters XBridge C18Chromatographic column, specification is 2.1mm × 150mm, i.d.3.5 μm；Mobile phase：A is
0.1% ammoniacal liquor, B is methanol；Isocratic elution：0~2min, A are that 10%, B is 90%；Flow is 0.30mLmin-1；Column temperature is
30℃；Sample size is 5 μ L；
Mass Spectrometry Conditions are：Negative electrospray ionization source；Capillary voltage is 2.5KV；Radio-frequency lens voltage is 0.5V；Ion source temperature
150℃；500 DEG C of solvent temperature degree is removed, solvent stream amount 500Lh is removed-1；Taper hole throughput 50Lh-1；Collision gas are pure
Argon gas of the degree not less than 99.999%, collision air pressure is 3.2 × 10-4kPa；Data acquisition scheme：Multiple-reaction monitoring；Bisphenol-A
Mass spectrometry parameters are：Retention time 1.30min；Monitor ion pair m/z (227.1/212.1) taper hole voltage 30V, collision energy
25eV；Monitor ion pair m/z (227.1/133.1) taper hole voltage 30V, collision energy 28eV.
9. research method according to claim 1, it is characterised in that：The compound method of the simulated sweat is：Weigh chlorine
Change sodium 5.0g, urea 1.0g, lactic acid 1.0g, after being dissolved with appropriate amount of deionized water, constant volume 1L, with 1% ammoniacal liquor adjust pH value be 6.5 ±
0.1；
It is described simulation saliva compound method be：Weigh Magnesium dichloride hexahydrate 0.17g, CALCIUM CHLORIDE DIHYDRATE 0.15g, three hydration phosphorus
One hydrogen potassium 0.76g, potassium carbonate 0.53g, sodium chloride 0.33g, potassium chloride 0.75g of acid, after being dissolved with appropriate amount of deionized water, constant volume
1L, adjusts pH value to be 6.8 ± 0.1 with 1% hydrochloric acid.
10. research method according to claim 1, it is characterised in that：The compound method of the bisphenol-A standard reserving solution：
The bisphenol-A standard substance that appropriate purity is not less than 98.5% is weighed, 0.1mg is accurate to, being configured to mass concentration with methanol is
1000mg·L-1Single Standard Stock solutions.
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