CN106596786A - Detection method for detecting organophosphate flame retardants in ABS plastic - Google Patents
Detection method for detecting organophosphate flame retardants in ABS plastic Download PDFInfo
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- CN106596786A CN106596786A CN201611214205.5A CN201611214205A CN106596786A CN 106596786 A CN106596786 A CN 106596786A CN 201611214205 A CN201611214205 A CN 201611214205A CN 106596786 A CN106596786 A CN 106596786A
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
The invention discloses a detection method for detecting organophosphate flame retardants in ABS plastic. The detection method at least comprises the following steps of 1 sample pretreating, wherein a to-be-detected sample is accurately weighed, crushed and dissolved, a hydrolytic agent-acetate solution is added, oscillating is conducted for 0.5 h to 2 h at room temperature, filtering is conducted, a to-be-detected sample solution is obtained, and a chitosan-cerium (IV) complex is adopted as the hydrolytic agent; 2 sample detecting, wherein the to-be-detected solution is detected with a gas chromatography-mass spectrometer, and qualitative and quantitative preliminary analysis is conducted on the to-be-detected solution; 3 sample re-detecting, wherein the to-be-detected solution is detected with 31P-NMP, and further qualitative and quantitative analysis is conducted on a result by combining an analysis result obtained in the step 2. According to the method, the organophosphate flame retardants in the ABS plastic can be quickly, conveniently and accurately detected.
Description
Technical field
The present invention relates to a kind of detection method, organophosphorus ester based flame retardant in more particularly to a kind of detection ABS plastic
Detection method.
Background technology
The fire retardant and fire proofing of today, is faced with from increasingly stricter fire safety standard and environmentally friendly rule
Double challenge.On the one hand, fire-protection standard provides wide development space to fire proofing, promotes the continuous of flame-retarded technology
Development；On the other hand, the release of environmentally friendly rule limits the application of some halogenated flame retardants.Comply with the requirement of safety and environmental protection development
It is principle that all plastic additive development and application business must follow forever, is adjusting the product knot of fire retardant always both at home and abroad
Structure, expects to develop high-performance safety and environmental protection fire retardant.Organic phosphorus flame retardant is the product for most possibly replacing halogenated flame retardant
One of kind, while the good anti-flammability of material and plasticising double effects are given, comparing with halogenated flame retardant has raw smoke for it
It is few, it is not easy to form the advantages such as toxic gas and corrosive gas.
But research in recent years shows, being excessively used organophosphorus ester based flame retardant (OPFRs) may be to human health, environment
Safety works the mischief；For this purpose, many countries and regions enact a law/regulation to be to limit uses of the OPFRs in various products.
At present conventional detection method is to be detected with conventional sense instrument again after Solid-Phase Extraction, but to reaction
This detection method Detection results of type organophosphorus ester based flame retardant are not ideal, there are technological difficulties.
For the problems referred to above, the present invention needs offer one kind badly and can quickly, conveniently, accurately detect organic phosphoric acid in ABS plastic
The method of esters fire retardant.
The content of the invention
For the problems referred to above, the present invention provides a kind of detection method of organophosphorus ester based flame retardant in detection ABS plastic,
Characterized in that, at least comprising the following steps：
(1) sample pretreatment：Testing sample is accurately weighed, is crushed, dissolving adds hydrolytic reagent acetum, shakes in room temperature
0.5～2h is swung, is filtered, obtain testing sample solution；
(2) sample detection：Solution to be measured is detected using gas chromatograph-mass spectrometer, prepare liquid is carried out it is qualitative and
Quantitative preliminary analyses；
(3) sample is detected again：Utilize31P-NMP is detected to solution to be measured, as a result with reference to the analysis result of step (2)
Further qualitative and quantitative analysis；
Wherein, hydrolytic reagent is shitosan cerium (IV) coordination compound.
In one embodiment, the hydrolytic reagent can also be aminoacid alkaline earth compoundses.
In one embodiment, the aminoacid alkaline earth compoundses are at least aminotriacetic acid magnesium complex, ammonia
One or more in base triacetic acid calcium composition.
In one embodiment, the aminoacid alkaline earth compoundses are aminotriacetic acid calcium composition.
In one embodiment, the hydrolytic reagent and the mass ratio of acetum are 1：(5～10).
In one embodiment, the hydrolytic reagent and the mass ratio of acetum are 1：(5～8).
In one embodiment, the gas phase condition is：
Gas chromatographic column：HP-1701 14%Cyanopropyl Phenyl Methyl Capillary30.0m × 320
μm×0.25μm；
Carrier gas：High pure nitrogen；
Input mode：Using Splitless injecting samples mode；
Sample size：1 μ l, it is qualitative with retention time, it is quantitative with sample peak area and standard comparing；
Gas flow rate：Hydrogen：75ml/min, air：100ml/min, make-up gas (nitrogen)：15ml/min；
Injector temperature：220℃；
Detector (FPD) temperature：250℃；
Column temperature program：100～120 DEG C of initial column temperature, constant temperature 2min；Then with the speed of 20～30 DEG C/min by column temperature liter
Up to 200～220 DEG C；Then, then with the speed of 1～6 DEG C/min column temperature is increased to into 240～280 DEG C.
In one embodiment, the Mass Spectrometry Conditions are：
Ion source：EI(70eV)；Ion temperature：230℃；Quadrupole rod temperature：150℃；Interface temperature：280℃；EM is electric
Pressure：1165V；Acquisition mode：SIM；The solvent delay time：3～4min；Tuning manner：Automatically tuning；Full ion scan scope：
50～500 μ.
In one embodiment, the column temperature program：120 DEG C of initial column temperature, constant temperature 2min；Then with 25 DEG C/min's
Column temperature is increased to 220 DEG C by speed；Then, then with the speed of 5 DEG C/min column temperature is increased to into 260 DEG C.
In one embodiment, it is described31P-NMP test conditions are as follows：D1 set of time be 30～60S, sweep time
For 4～12h, solvent is deuterochloroform.
With reference to above-mentioned and other features, aspect and the advantage that the present invention is more readily understood described further below.
Figure of description
Fig. 1：PFR-A31P-NMP collection of illustrative plates
Fig. 2：PFR-B31P-NMP collection of illustrative plates
Fig. 3：PFR-D31P-NMP collection of illustrative plates
Fig. 4：PFR-F31P-NMP collection of illustrative plates
Specific embodiment
The participation in the election detailed description for being preferable to carry out method of the invention below and including embodiment this can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " including ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily solely those key elements, and can be including not expressly listed other key elements or
The intrinsic key element of this kind of compositionss, step, method, product or device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If in being used for claim, this
Phrase will make claim for closed so as to not comprising the material in addition to the material that those are described, but it is relative often
Except rule impurity.When phrase " Consists of " is occurred in be rather than immediately following after theme in the clause of claim main body,
It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this is appreciated that and specifically discloses by any range limit or preferred value and any scope
All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numerical range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers within the range and fraction.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or " arbitrarily
It is a kind of " refer to that the item for describing thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this concrete
Quantity, also includes the acceptable part without causing the amendment of the change of related basic function being close to the quantity.Phase
Answer, with " about ", a numerical value of the modification such as " about ", mean and the invention is not restricted to the exact numerical.In some examples, approximately
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with
Combine and/or exchange, if not stated otherwise these scopes include all subranges contained therebetween.
Additionally, key element of the present invention or indefinite article " one kind " and " one " before component are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also includes plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means the polymerizable compound prepared by the monomer by the identical or different type that is polymerized.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer prepared by least two different monomers that are polymerized.Generic term " copolymer " includes
(its is general with term " terpolymer " for term " copolymer " (it is typically to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It is also comprising the polymer manufactured by the more kinds of monomers of polymerization.
" blend " means the polymer that two or more polymer is mixed and formed jointly by physics or chemistry method.
After polymeric material is heated, temperature gradually rises, and the key of some stability differences starts fracture；Decomposition is reached when being heated
During temperature, most of keys rupture in polymer, start to decompose.The thermal decomposition of polymer is an endothermic process, absorption
Heat necessarily be greater than the bond energy of main chain, so, decompose from the beginning of at most weak bond, it is seen that, the decomposition of polymer is tied by materials chemistry
Structure is determined.Polymer constantly cracks the product for ultimately producing may following several：Fuel gas (methane, ethylene etc.), does not fire
Gas (N2、NH3, hydrogen halides etc.), liquid (molten polymer, tar etc.).Solid (carbide etc.), (what is suspended in air consolidates cigarette
Body microgranule).Have a certain impact with the presence or absence of thermal decomposition of the oxygen to polymer:During anaerobic thermal decomposition (thermal cracking), C-C bond fissions
It is carbon from mountain base or holds alkene, decomposition temperature is mainly related to main chain C-C bond energys:During aerobic thermal decomposition (thermal oxide decomposition), mainly
Hydrogen or hydroxyl free radical are produced, while there is cross-linking reaction, stability can be related to c h bond.
Because the chemical constitution of most of polymeric material is made up of carbon, hydrogen skeleton, it is doomed it and easily burns, combustion reaction
Including two factors:Combustible and oxidizer (oxygen).Whole combustion process provides energy, surface of polymer material liter from thermal source
Temperature starts, and when temperature be enough to make polymer chemistry bond fission, polymeric material discharges scission fragments in air, often this
A little small molecule chemicals are all fuel gas, when ambient temperature reaches burning-point (flash-point) of these fuel gas, start combustion
Burn, heat release；Heat further decomposes polymer, and this process is constantly reciprocal, it is seen that, the length of combustion period, depending on can
Combustion gas body combustion heat release amount.When thermal discharge can produce new combustible, burning continues；When thermal discharge be not enough to produce it is new
During decomposition, fire end.This process is vividly described as polymeric material fuel element model.The burning of polymeric material
5 stages can be divided again in time:Ignite, flame propagation, burning, raw cigarette and self-extinguishment.But, actually, this process is very
Complexity, including numerous reactions and heat transfer phenomenon.Oxidation occurs in gas phase, be cracking combustible with oxygen in polymer surfaces
Vigorous reaction, produce free radical and simultaneously start burning.Pilot stage is especially affected by oxygen concentration, and combustion heat release makes polymer
Further decompose, so, even if without external heat source, burning may continue to.
Plastics ABS resin is that current production rate is maximum, most widely used polymer, and it is by PB, the various performances of PAN, PS
Organically unite, have concurrently it is tough, firmly, just mutually excellent mechanical property in a balanced way.ABS is acrylonitrile, butadiene and cinnamic
Terpolymer, A represents acrylonitrile, and B represents butadiene, and S represents styrene.Due to constituting with three kinds, and impart it very
Good performance；Acrylonitrile gives chemical stability, oil resistivity, certain rigidity and the hardness of ABS resin；Butadiene makes its tough
Property, impact and tolerance to cold increase；Styrene makes it have good dielectric properties, and good processability is presented.
Most of ABS is nontoxic, and waterproof, but slightly moisture vapor permeable, water absorption rate is low, and the room temperature 1 year water absorption rate that soaks does not surpass
Cross 1% and physical property does not change.ABS resin product surface can be polished, and can obtain press polished product.
ABS has excellent comprehensive physical and mechanical performance, fabulous low-temperature impact resistance.Dimensional stability.Electrically
Energy, wearability, chemical proof, dyeability, finished product processing and machining are preferable.ABS resin is water-fast, inorganic salt, alkali and
Acids, insoluble in most of alcohols and varsol,
Fire retardant (flameretardant) is to improve material flame resistance, that is, prevent material from being ignited and suppress flame
The auxiliary agent of propagation.Fire retardant be mainly used in synthesize and natural macromolecular material it is fire-retardant (including plastics, rubber, fiber, timber,
Paper, coating etc., but mainly plastics).Compared with not fire-retardant same type of material, the former is difficult to be drawn material containing fire retardant
Combustion, can suppress flame propagation, can prevent small fire from developing into catastrophic big fire, substantially reduce fire hazard, contribute to various
The use of product safety.
In order to solve above-mentioned technical problem, the present invention provides organophosphorus ester based flame retardant in a kind of detection ABS plastic
Detection method, it is characterised in that at least comprise the following steps：
(1) sample pretreatment：Testing sample is accurately weighed, is crushed, dissolving adds hydrolytic reagent acetum, shakes in room temperature
0.5～2h is swung, is filtered, obtain testing sample solution；
(2) sample detection：Solution to be measured is detected using gas chromatograph-mass spectrometer, prepare liquid is carried out it is qualitative and
Quantitative preliminary analyses；
(3) sample is detected again：Utilize31P-NMP is detected to solution to be measured, as a result with reference to the analysis result of step (2)
Further qualitative and quantitative analysis；
Wherein, hydrolytic reagent is shitosan cerium (IV) coordination compound.
Reactive flame retardant includes flame-retardant monomer and flame retardant curing agent, and they form chemical bond with polymeric material matrix,
Material inherent flame retardancy is given, the weak point of additive flame retardant is fundamentally avoided.It is fire-retardant for thermoplastic
Monomer, different from add phosphorus containing flame retardant, reactive organophosphorous fire retardant is presented condensed phase fire retardation.
Below the synthetic method of predominantly organic phosphate ester flame retardants PFR-A, PFR-B, PFR-P and PFR-D is as follows：
The synthesis of SPDPC
Lmol tetramethylolmethanes, (2.2mol) phosphorus oxychloride and 1000mL methylene chlorides are added in flask. heating is stirred
Mix, react till emerging without HCL, cross filtered product and washed with dichloromethane, absolute ether successively, obtain after being dried
Product, is white powdery solids.
The synthesis of MDCT
100ml methanol and C are added in flask3N3Cl3(0.02mol), by adding NaHC03To adjust pH, and keep
5 or so, after reaction terminates, filter, be dried, sublimation purification obtains white crystalline solid.
The synthesis of PFR-A
Piperazine anhydrous (0.1mol) and 100mL second eyeballs are added to 250ml reaction bulbs, after being completely dissolved, SPDPC is added
(0.1mol) with MDCT (0.1mol), Deca 0.22mol triethylamine in 2 hours, the lower backflow of nitrogen protection 6 hours, what is obtained is white
Color fine sand shape product after washing, is dried.
The synthesis of PFR-B
(0.11mol and 100mL second eyeballs after being completely dissolved, are added to add Piperazine anhydrous tetrabromobisphenol A to 250ml reaction bulbs
SPDPC (0.11mol) and MDCT (0.11mol), Deca triethylamine (0.22mol) in 2 hours, the lower backflow of nitrogen protection 6 hours,
The white fine sand shape product for obtaining after washing, is dried.
The synthesis of PFR-P
(1) synthesis of 1- oxos-methylol -1- phosphas -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane (PEPA)
0.2mol tetramethylolmethanes (PER) and 50ml dioxane are sequentially added equipped with constant pressure funnel, agitator, temperature
In the four-hole bottle of degree meter and reflux condensing tube (tail end with connect equipped with anhydrous calcium chloride drying tube and hydrogen chloride absorption liquid phase), heat
90 DEG C are warming up to, 0.2mol phosphorus oxychloride is slowly added dropwise under agitation, temperature rising reflux 3-4 hours after completion of dropping, reaction terminates
Cooling being stood afterwards, being filtered after solid is separated out completely, obtain PEPA crude products, heat is dissolved in after crude product is washed with dioxane
Carry out recrystallization in ethanol, and be dried at 50 DEG C of vacuum drying oven, the white solid for obtaining be pentaerythritol phosphate-
PEPA。
(2) synthesis of PFR-P
0.2molPEPA is added to be had in the 500mL there-necked flasks of 200mL second eyeballs, dispersed with stirring, by lmolPOCl3Slowly
Add, stirring, temperature reaction, to overflowing without HCI, the distillation that heats up removes the POCl of solvent and excess3, bisphenol S is subsequently adding,
Progressively heat up under nitrogen stream, stir, control to be reacted at 140-260 DEG C, to guarantee progressively carrying out and producing for polycondensation reaction
HCl gases are discharged in time, and pale-yellow galss shape product is obtained final product after cooling:PFR-P.
The synthesis of PFR-D
(1)DOPO-CH2The synthesis of OH
0.2molDOPO and 100ml ethanol is added constant pressure funnel, agitator, thermometer and reflux condensing tube are housed
Four-hole bottle in, be heated to 70 DEG C, be slowly added dropwise 20g37% formalins under agitation, 30min completion of dropping rises
Temperature backflow 6 hours, reaction stands cooling after terminating, and filters after solid is separated out completely, is dried at 50 DEG C of vacuum drying oven, obtains
DOPO-CH2OH。
(2) synthesis of PFR-D
By DOPO-CH2OH 0.2mol and POCl3150ml reacts 2 hours at 60 DEG C of oil bath, condition be mechanical agitation simultaneously
Logical nitrogen protection, wherein excess POCl3Serve as solvent, obtain excessive POCl after intermediate3Steam, be cooled to 50 DEG C of additions
0.2mol bisphenol S 50g, are slowly stirred and are warming up to 120 DEG C of systems softenings, and HCl is steamed, and are warming up to 260 DEG C of reaction 4-8 hours,
Pour out while hot, product is yellowish transparent glassy solid, is ground after cooling, be dried, obtain PFR-D.
Crush, just refer to the process of that material size reduces.Various types of crushing mechanisms are generally adopted, material is applied not
Complete with mechanical force, such as tensile force, extruding force, impulsive force and shearing force.The crushing of high impact polystyrene can be
Crush, smash, grind or shred.
Crushing be material be squeezed power effect it is crushed, the mode of crushing can be the gold for using two pieces of relative motioies
Category plate is mutually extruded, or rotates against rolling, or making in outer conically shaped of inner cone for rod using two
Eccentric rotary is extruding.
It is that material is crushed by outer impact force action to smash, and the mode for smashing can be beating for external hard objects
Hit, or material itself between and it is mutual and the generation high speed impact, or material of fixed hard steel plate between
Clash into.
Grind be material rolled between different shape abrasive body effect and it is crushed.
Shred crushed under the effect such as shearing, puncture, tear for being material in sharp weapon such as blades.
Crushing can also be freezing and pulverizing.Can include for example using liquid nitrogen as abrasive media, using freezing crusher
For high impact polystyrene carries out freezing and pulverizing.
Rare earth ion also has the ability of fracture phosphoric acid ester bond.Most of rare earth there is hydrolytic cleavage to make phosphodiester bond
With, wherein it is the strongest with the effect of cerium ion, tetravalent state may be easily formed in solution system with trivalent cerium relevant.By
It is stronger with the coordination ability of oxygen, sulfur, nitrogen-atoms in rare earth ion, it is a kind of excellent lewis acid, its ligancy is up to 12,
Under near-neutral sulfite deinking, stable rare earth compounding can be formed.
Organophosphors contain three phosphides is good for, so being commonly referred to as phosphotriester, water-disintegrable fracture is only by some di-phosphate esters
There is water-disintegrable cutting in key, the fracture fragment of generation is typically stickiness.However, the intrinsic stability of phosphodiester bond is allowed to remove
Could occur under phosphoesterase action that effectively fracture is outer, to occur non-enzymatic catalysis water-disintegrable fracture exist it is greatly tired
It is difficult.Ce (IV) can make deoxynucleotide dimer dApdA rupture.Strikingly, generally using the anti-of Ce (III)
Ying Zhong, needs O2Nucleotide dimer can be just set to rupture；And Ce (IV) is not required to O2, and the product for obtaining belongs to hydrolyzate
And nonoxidative products, illustrate Ce (IV) can catalytic nucleic acid phosphodiester bond hydrolyze.
Contain substantial amounts of hydroxyl (- OH), amino (- NH in chitosan molecule2) or acylamino- (- NHCOCH3), from conformation
From the point of view of, they are all equatorial bonds, and this special construction causes them to carry out complexation reaction shape with transition metal and alkaline-earth metal
Into coordination compound, naturally become the object of study with metallic ion coordination.
Chitosan metal complexes have some architectural features of native enzyme, and such as molecular weight is larger, contain metal ion, control
Condition processed can obtain sequestration circulus, thus show fabulous catalysis activity to many chemical reactions.
Cerium ion has the effect for sterilizing and rupturing phosphoric acid ester bond, and shitosan is easy to be formed with metal combination lives with catalysis
The coordination compound of property.
The preparation of shitosan cerium (IV) coordination compound：
0.5g ammonium ceric nitrates, 100ml0.5% acetums are added in 250ml there-necked flasks, is sufficiently stirred for, added
0.5g shitosans, stirring until completely dissolved, continues to stir and adjust PH to 5.0, continues to stir 5h, after reaction terminates, mistake
Filter, drip washing is carried out with 20ml ethanol, and 40 DEG C of drying under reduced pressure obtain shitosan cerium (IV) coordination compound.
In one embodiment, the hydrolytic reagent can also be aminoacid alkaline earth compoundses.
The hydrolysis of phosphoric acid ester bond is also individual nucleophilic substitution process, and first, nucleophilic species hydroxide ion (is lived by metal ion
Hydrone dissociation after change is produced) attack phosphorus atoms, a pentacoordinate intermediate is formed, this step is reversible；Second step,
P-O keys rupture, and product is generated.Research finds, second step reaction, i.e. the fracture of P-O keys is rate-limiting step, Ke Yitong
Cross and increase the formation constantc1 or stability of pentacoordinate intermediate to improve the reaction rate of this step.Due to P-O bond polarities compared with
By force, phosphorus atoms can band part positive electricity.Reaction starts, and nucleophilic species hydroxyl attacks the phosphorus atoms of positively charged, in forming pentacoordinate
Mesosome.The pentacoordinate body structure of phosphorus atoms takes the coordination structure of trigonal biyramid shape, and 3 on the equatoriat plane P-O keys are shorter, explanation
Combination is stronger, is assumed to be sp2Hydridization, wherein there is an oxygen atom to be directly coordinated with Mg (II) ion；2 P- of axial direction
O keys are longer, illustrate, with reference to weaker, to be assumed to be rectilinear pzdz2Hydridization.In sum, magnesium ion rises in hydrolysis
Two kinds of effects of key are arrived：1st, activated water molecule produces nucleophilic species hydroxyl；2nd, stable pentacoordinate intermediate.
Mg2+It is the less ion of atomic radius, is easy to attract hydrone, therefore actually Mg2+Group radius is larger, Mg2+
Six coordinate bonds bond length and bond angle more fix；Mg2+It is especially sour with reference to neutral nitrogen-containing group such as aminoacid and imidazoles
Oxygen in property group.
Aminotriacetic acid outward appearance is white prismatic crystallization or powder, can not be total to strong oxidizer, aluminum, copper, copper alloy and nickel
Deposit.Aminotriacetic acid can provide four coordinate bonds for metal ion, and its molecule is again less, thus it have it is very strong
Complexing power, can form stable chelate with each metal ion species.
In one embodiment, the aminoacid alkaline earth compoundses are at least aminotriacetic acid magnesium complex, ammonia
One or more in base triacetic acid calcium composition.
In one embodiment, the aminoacid alkaline earth compoundses are aminotriacetic acid calcium composition.
The preparation method of aminotriacetic acid calcium composition and aminotriacetic acid magnesium complex：
1mol aminotriacetic acids and 0.8mol basic magnesium carbonate (Phe are added in 300ml purified water:Mg2+=1:0.35),
Stir 5h under the conditions of 90 DEG C, condensing reflux, in order to prevent high temperature under oxidation reaction, whole reaction carries out under nitrogen protection anti-
Should, after reaction terminates, product centrifuging and taking supernatant, rotary evaporation stands overnight and treats that crystal is slowly analysed to there is granule crystal to occur
Go out, filter after separating out completely, with ethanol and acetone (1:2) mixing organic reagent (20ml*3) is washed three times, vacuum drying, is put
Put in exsiccator and save backup.
The preparation method of aminotriacetic acid calcium composition with aminotriacetic acid magnesium complex preparation method.
In one embodiment, the hydrolytic reagent and the mass ratio of acetum are 1：(5～10).
In one embodiment, the hydrolytic reagent and the mass ratio of acetum are 1：(5～8).
In one embodiment, the microporous filter membrane is polytetrafluoroethylfiber fiber film, and the aperture of the microporous filter membrane is
0.5μm。
PTFE for tetrafluoroethene (TFE) monomer high crystallinity polymer, it is nonpoisonous and tasteless, its molecular structure unit formula for-(-
CF2-CF2-)n-.Strand is formed by two kinds of elements of fluorine carbon by Covalent bonding together.PTFE and polyethylene (PE) strand very phase
Seemingly, but, the fluorine atom volume in PTFE is larger, and the negative charge of adjacent fluorine atom is mutually exclusive so that strand is in space
On helically conformation, and form a closely protective layer of " fluoro " completely.Fluorine atom has high chemical inertness so that
PTFE becomes minimum, the incomparable chemical stability of surface energy.
The bond energy of the C-C keys of PTFE is 332kJ mol-1, C-F keys bond energy is 485kJ mol-1, bond energy is relatively strong, therefore
Intramolecular is firmly combined with, and heat stability is good, can in the range of -196 DEG C～260 DEG C life-time service.However, due to C-F keys pole
It does not firmly provide the ability needed for C-F bond fissions in tetrafluoroethene (TFE) monomer polymerization process, therefore can not produce
Chain structure so that PTFE has higher degree of crystallinity.
It is negatively charged because the bond energy of C-F keys is very high and the constraint of fluorine atom verification electron outside nucleus and bonding electronss cloud is strong
The mutually exclusive formation of fluorine atom helical conformation.The intermolecular packing density of politef is larger, and this allows for various examinations
Agent is difficult to go deep in the middle of strand.So, the nonpolar and crystalline texture of this screw type complete " fluoro " PTFE molecules in addition makes
Obtain PTFE and possess extremely excellent chemical resistance.
PTFE can be born in addition to the sodium hydroxide except molten alkali metal, element fluorine and strong fluorinated dielectric and higher than 300 DEG C
Strong acid and strong base, strong oxidizer, reducing agent etc. effect, or even in the chloroazotic acid for boiling, the quality and performance of PTFE all do not have yet
There is any change.
In addition, the electronegativity of fluorine atom is greatly, tetrafluoroethylene monomer has perfect symmetry and makes PTFE intermolecular
Captivation and surface energy are relatively low, so that preferable ductility when PTFE has extremely low skin-friction coefficient and low temperature.
PTFE fiber has excellent resistance to chemical attack and resistance to elevated temperatures, can apply in high temperature air filtration field.
PTFE surface free energy very littles, surface tension only has 0.019N/m, is a kind of minimum solid material of current surface energy, existing
Solid material cannot nearly all stick to its surface.
In one embodiment, the gas phase condition is：Gas chromatographic column：HP-1701 14%Cyanopropyl
Phenyl Methyl Capillary 30.0m×320μm×0.25μm；
Carrier gas：High pure nitrogen；
Input mode：Using Splitless injecting samples mode；
Sample size：1 μ l, it is qualitative with retention time, it is quantitative with sample peak area and standard comparing；
Gas flow rate：Hydrogen：75ml/min, air：100ml/min, make-up gas (nitrogen)：15ml/min；
Injector temperature：220℃；
Detector (FPD) temperature：250℃；
Column temperature program：100～120 DEG C of initial column temperature, constant temperature 2min；Then with the speed of 20～30 DEG C/min by column temperature liter
Up to 200～220 DEG C；Then, then with the speed of 1～6 DEG C/min column temperature is increased to into 240～280 DEG C.
In one embodiment, the Mass Spectrometry Conditions are：
Ion source：EI(70eV)；Ion temperature：230℃；Quadrupole rod temperature：150℃；Interface temperature：280℃；EM is electric
Pressure：1165V；Acquisition mode：SIM；The solvent delay time：3～4min；Tuning manner：Automatically tuning；Full ion scan scope：
50～500 μ.
In one embodiment, the column temperature program：120 DEG C of initial column temperature, constant temperature 2min；Then with 25 DEG C/min's
Column temperature is increased to 220 DEG C by speed；Then, then with the speed of 5 DEG C/min column temperature is increased to into 260 DEG C.
In one embodiment, the solvent delay time：3.6min.
In one embodiment, it is described31P-NMP test conditions are as follows：D1 set of time be 30～60S, sweep time
For 4～12h, solvent is deuterochloroform.
Organophosphorus ester based flame retardant is different from inorganic phosphorus fire retardant, and organophosphorus compoundses flame retardant molecule amount is big, have one
The fixed degree of polymerization, after being blended with ABS resin, can produce and be intertwined, and detect with after solvent extraction, general detection knot
Fruit is not necessarily accurate.
The present invention is mainly cracked by hydrolytic reagent to organophosphorus ester based flame retardant, by organophosphorus compoundses macromole
It is hydrolyzed into after small molecule and is detected with conventional instrument again, reaches and the qualitative and quantitative of organophosphorus ester in fire retardant is divided
Analysis.
The present invention is specifically described below by embodiment.Be necessary it is pointed out here that, following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
According to some nonessential modifications and adaptations that the content of the invention described above is made, protection scope of the present invention is still fallen within.
In addition, if without other explanation, it is raw materials used be all it is commercially available, be purchased from traditional Chinese medicines chemical reagent.
Embodiment 1
The detection method of organophosphorus ester based flame retardant, comprises the following steps in a kind of detection ABS plastic：
(1) sample pretreatment：1.0g testing samples are accurately weighed, is crushed, then dissolved using tetrahydrofuran (10ml), drop
Plus hydrolytic reagent aminotriacetic acid magnesium complex acetum (0.18g/ml, 5ml), in shaken at room temperature 1h, then vibration terminates, uses
0.5 μm of expanded microporous polytetra fluoroethylene-EPTEE Fibrous membrane filtration, obtains testing sample solution；
(2) sample detection：The organophosphorus ester based flame retardant in solution to be measured is examined using gas chromatograph-mass spectrometer
Survey；Wherein chromatographic condition is：
Gas chromatographic column：HP-701 14%Cyanopropyl Phenyl Methyl Capillary30.0m × 320 μm
×0.25μm；Carrier gas：High pure nitrogen；Input mode：Using Splitless injecting samples mode；Sample size：1 μ l, it is qualitative with retention time,
It is quantitative with sample peak area and standard comparing；Gas flow rate：Hydrogen：75ml/min, air：100ml/min, make-up gas (nitrogen
Gas)：15ml/min；Injector temperature：220℃；Detector (FPD) temperature：250℃；Column temperature program：120 DEG C of initial column temperature, it is permanent
Warm 2min；Then column temperature is increased to into 220 DEG C with the speed of 25 DEG C/min；Then, then with the speed of 5 DEG C/min by column temperature liter
Up to 260 DEG C.
Mass Spectrometry Conditions are：Ion source：EI(70eV)；Ion temperature：230℃；Quadrupole rod temperature：150℃；Interface temperature：
280℃；EM voltages：1165V；Acquisition mode：SIM；The solvent delay time：3.6min；Tuning manner：Automatically tuning；Full ion
Sweep limitss：50～500 μ.
(3) sample is detected again：Utilize31P-NMP is detected to solution to be measured, as a result with reference to step (2)
The further qualitative and quantitative analysis of analysis result；
31P-NMP testing conditions are：D1 set of time is 50S, and sweep time is 10h, and solvent is deuterochloroform.
The phosphorus flame retardant for being detected is：PFR-A；Measured with internal standard method as internal standard substance using dibutyl phthalate
PFR-A contents in ABS plastic were 10.6% (PFR-A contains 10.6% in testing sample)；With deuterochloroform as solvent, core
Magnetic phosphorus spectrum chemical shift δ (ppm) be：12.01ppm, as shown in Figure 1.
Embodiment 2
The detection method of organophosphorus ester based flame retardant, comprises the following steps in a kind of detection ABS plastic：
(1) sample pretreatment：1.0g testing samples are accurately weighed, is crushed, then dissolved using tetrahydrofuran (10ml), drop
Plus hydrolytic reagent aminotriacetic acid magnesium complex acetum (0.18g/ml, 5ml), in shaken at room temperature 1h, then vibration terminates, uses
0.5 μm of expanded microporous polytetra fluoroethylene-EPTEE Fibrous membrane filtration, obtains testing sample solution；
(2) sample detection：The organophosphorus ester based flame retardant in solution to be measured is examined using gas chromatograph-mass spectrometer
Survey, the then qualitative and quantitative analysis according to testing result to organophosphorus ester based flame retardant；Wherein chromatographic condition is：
Gas chromatographic column：HP-701 14%Cyanopropyl Phenyl Methyl Capillary30.0m × 320 μm
×0.25μm；Carrier gas：High pure nitrogen；Input mode：Using Splitless injecting samples mode；Sample size：1 μ l, it is qualitative with retention time,
It is quantitative with sample peak area and standard comparing；Gas flow rate：Hydrogen：75ml/min, air：100ml/min, make-up gas (nitrogen
Gas)：15ml/min；Injector temperature：220℃；Detector (FPD) temperature：250℃；Column temperature program：120 DEG C of initial column temperature, it is permanent
Warm 2min；Then column temperature is increased to into 220 DEG C with the speed of 25 DEG C/min；Then, then with the speed of 5 DEG C/min by column temperature liter
Up to 260 DEG C.
Mass Spectrometry Conditions are：Ion source：EI(70eV)；Ion temperature：230℃；Quadrupole rod temperature：150℃；Interface temperature：
280℃；EM voltages：1165V；Acquisition mode：SIM；The solvent delay time：3.6min；Tuning manner：Automatically tuning；Full ion
Sweep limitss：50～500 μ.
(3) sample is detected again：Solution to be measured is detected using 31P-NMP, as a result with reference to the analysis result of step (2)
Further qualitative and quantitative analysis；
31P-NMP testing conditions are：D1 set of time is 50S, and sweep time is 10h, and solvent is deuterochloroform.
The phosphorus flame retardant for being detected is：PFR-B；Measured with internal standard method as internal standard substance using dibutyl phthalate
PFR-B contents in ABS plastic are 7.1% (PFR-B has 7.1% in testing sample), with deuterochloroform as solvent, nuclear-magnetism phosphorus
The chemical shift δ (ppm) of spectrum is：10.7ppm, as shown in Figure 2.
Embodiment 3
The detection method of organophosphorus ester based flame retardant, comprises the following steps in a kind of detection ABS plastic：
(1) sample pretreatment：1.0g testing samples are accurately weighed, is crushed, then dissolved using tetrahydrofuran (10ml), drop
Plus hydrolytic reagent aminotriacetic acid magnesium complex acetum (0.18g/ml, 5ml), in shaken at room temperature 1h, then vibration terminates, uses
0.5 μm of expanded microporous polytetra fluoroethylene-EPTEE Fibrous membrane filtration, obtains testing sample solution；
(2) sample detection：The organophosphorus ester based flame retardant in solution to be measured is examined using gas chromatograph-mass spectrometer
Survey, the then qualitative and quantitative analysis according to testing result to organophosphorus ester based flame retardant；Wherein chromatographic condition is：
Gas chromatographic column：HP-701 14%Cyanopropyl Phenyl Methyl Capillary30.0m × 320 μm
×0.25μm；Carrier gas：High pure nitrogen；Input mode：Using Splitless injecting samples mode；Sample size：1 μ l, it is qualitative with retention time,
It is quantitative with sample peak area and standard comparing；Gas flow rate：Hydrogen：75ml/min, air：100ml/min, make-up gas (nitrogen
Gas)：15ml/min；Injector temperature：220℃；Detector (FPD) temperature：250℃；Column temperature program：120 DEG C of initial column temperature, it is permanent
Warm 2min；Then column temperature is increased to into 220 DEG C with the speed of 25 DEG C/min；Then, then with the speed of 5 DEG C/min by column temperature liter
Up to 260 DEG C.
Mass Spectrometry Conditions are：Ion source：EI(70eV)；Ion temperature：230℃；Quadrupole rod temperature：150℃；Interface temperature：
280℃；EM voltages：1165V；Acquisition mode：SIM；The solvent delay time：3.6min；Tuning manner：Automatically tuning；Full ion
Sweep limitss：50～500 μ.
(3) sample is detected again：Utilize31P-NMP is detected to solution to be measured, as a result with reference to the analysis result of step (2)
Further qualitative and quantitative analysis；
31P-NMP testing conditions are：D1 set of time is 50S, and sweep time is 10h, and solvent is deuterochloroform.
The phosphorus flame retardant for being detected is：PFR-D；Measured with internal standard method as internal standard substance using dibutyl phthalate
PFR-D contents in ABS plastic were 5.6% (PFR-D contains 5.6% in testing sample)；With deuterated dichloromethane as solvent,
Nuclear-magnetism phosphorus spectrum chemical shift δ (ppm) be：7.6ppm, 11.2ppm, as shown in Figure 3.
Embodiment 4
The detection method of organophosphorus ester based flame retardant, comprises the following steps in a kind of detection ABS plastic：
(1) sample pretreatment：1.0g testing samples are accurately weighed, is crushed, then dissolved using tetrahydrofuran (10ml), drop
Plus hydrolytic reagent aminotriacetic acid magnesium complex acetum (0.18g/ml, 5ml), in shaken at room temperature 1h, then vibration terminates, uses
0.5 μm of expanded microporous polytetra fluoroethylene-EPTEE Fibrous membrane filtration, obtains testing sample solution；
(2) sample detection：The organophosphorus ester based flame retardant in solution to be measured is examined using gas chromatograph-mass spectrometer
Survey, it is then fire-retardant to determine corresponding organophosphorus compoundses according to the standard curve obtained in testing result and step (1)
The qualitative and quantitative analysis of agent；Wherein chromatographic condition is：
Gas chromatographic column：HP-701 14%Cyanopropyl Phenyl Methyl Capillary30.0m × 320 μm
×0.25μm；Carrier gas：High pure nitrogen；Input mode：Using Splitless injecting samples mode；Sample size：1 μ l, it is qualitative with retention time,
It is quantitative with sample peak area and standard comparing；Gas flow rate：Hydrogen：75ml/min, air：100ml/min, make-up gas (nitrogen
Gas)：15ml/min；Injector temperature：220℃；Detector (FPD) temperature：250℃；Column temperature program：120 DEG C of initial column temperature, it is permanent
Warm 2min；Then column temperature is increased to into 220 DEG C with the speed of 25 DEG C/min；Then, then with the speed of 5 DEG C/min by column temperature liter
Up to 260 DEG C.
Mass Spectrometry Conditions are：Ion source：EI(70eV)；Ion temperature：230℃；Quadrupole rod temperature：150℃；Interface temperature：
280℃；EM voltages：1165V；Acquisition mode：SIM；The solvent delay time：3.6min；Tuning manner：Automatically tuning；Full ion
Sweep limitss：50～500 μ.
(3) sample is detected again：Utilize31P-NMP is detected to solution to be measured, as a result with reference to the analysis result of step (2)
Further qualitative and quantitative analysis；
31P-NMP testing conditions are：D1 set of time is 50S, and sweep time is 10h, and solvent is deuterochloroform.
The phosphorus flame retardant for being detected is：PFR-P；Measured with internal standard method as internal standard substance using dibutyl phthalate
PFR-P contents in ABS plastic were 6.1% (PFR-P contains 6.1% in testing sample)；With deuterated dichloromethane as solvent,
Nuclear-magnetism phosphorus spectrum chemical shift δ (ppm) be：8.8ppm, 12.5ppm, as shown in Figure 4.
Embodiment 5
Detection method and step such as embodiment 1, is distinguished as hydrolytic reagent for shitosan cerium (IV) coordination compound acetum
(0.1g/ml,5ml)。
The phosphorus flame retardant for being detected is：PFR-A；Measured with internal standard method as internal standard substance using dibutyl phthalate
PFR-A contents in ABS plastic were 8.7% (PFR-A contains 10.6% in testing sample)；With deuterochloroform as solvent, core
Magnetic phosphorus spectrum chemical shift δ (ppm) be：12.0ppm.
Embodiment 6
Detection method and step such as embodiment 1, is distinguished as hydrolytic reagent for aminotriacetic acid calcium composition acetum.Examined
The phosphorus flame retardant of survey is：PFR-P (PFR-P contains 6.1% in testing sample)；Using dibutyl phthalate as internal standard substance
It is 5.9% to measure PFR-P contents in ABS plastic with internal standard method；With deuterated dichloromethane as solvent, the chemistry of nuclear-magnetism phosphorus spectrum
Displacement δ (ppm) is：8.8ppm, 12.5ppm.
Embodiment 7
Detection method and step such as embodiment 6, is distinguished as31P-NMP test conditions are as follows：D1 set of time is 30S, is scanned
Time is 4h.
The phosphorus flame retardant for being detected is：PFR-P；Measured with internal standard method as internal standard substance using dibutyl phthalate
PFR-P contents in ABS plastic were 5.3% (PFR-P contains 6.1% in testing sample)；With deuterated dichloromethane as solvent,
Nuclear-magnetism phosphorus spectrum chemical shift δ (ppm) be：8.7ppm, 12.3ppm.
Embodiment 8
Detection method and step such as embodiment 1, is distinguished as hydrolytic reagent for shitosan cerium (IV) coordination compound acetum.
The phosphorus flame retardant for being detected is：PFR-P；Measured with internal standard method as internal standard substance using dibutyl phthalate
PFR-P contents in ABS plastic were 5.0% (PFR-P contains 6.1% in testing sample)；With deuterated dichloromethane as solvent,
Nuclear-magnetism phosphorus spectrum chemical shift δ (ppm) be：8.9ppm, 12.6ppm.
Embodiment 9
Detection method and step such as embodiment 2, is distinguished as31P-NMP test conditions are as follows：D1 set of time is 30S, is scanned
Time is 4h.
The phosphorus flame retardant for being detected is：PFR-B；Measured with internal standard method as internal standard substance using dibutyl phthalate
PFR-B contents in ABS plastic are 5.0% (PFR-B has 7.1% in testing sample), with deuterochloroform as solvent, nuclear-magnetism phosphorus
The chemical shift δ (ppm) of spectrum is：10.8ppm.
Embodiment 10
Detection method and step such as embodiment 2, is distinguished as31P-NMP test conditions are as follows：D1 set of time is 30S, is scanned
Time is 4h.
The phosphorus flame retardant for being detected is：PFR-D；Measured with internal standard method as internal standard substance using dibutyl phthalate
PFR-D contents in ABS plastic were 4.2% (PFR-D contains 5.6% in testing sample)；With deuterated dichloromethane as solvent,
Nuclear-magnetism phosphorus spectrum chemical shift δ (ppm) be：7.6ppm, 11.2ppm.
Embodiment 11
Detection method and step such as embodiment 2, is distinguished as31P-NMP test conditions are as follows：D1 set of time is 60S, is scanned
Time is 4h.
The phosphorus flame retardant for being detected is：PFR-D；Measured with internal standard method as internal standard substance using dibutyl phthalate
PFR-D contents in ABS plastic were 5.5% (PFR-D contains 5.6% in testing sample)；With deuterated dichloromethane as solvent,
Nuclear-magnetism phosphorus spectrum chemical shift δ (ppm) be：7.4ppm, 11.1ppm.
Comparative example 1
The detection method of organophosphorus ester based flame retardant, comprises the following steps in a kind of detection ABS plastic：
(1) sample pretreatment：1.0g testing samples are accurately weighed, is crushed, then dissolved using tetrahydrofuran (10ml), in
Shaken at room temperature 1h, then vibration terminates, and with 0.5 μm of expanded microporous polytetra fluoroethylene-EPTEE Fibrous membrane filtration, obtains testing sample solution；
(2) sample detection：The organophosphorus ester based flame retardant in solution to be measured is examined using gas chromatograph-mass spectrometer
Survey, the then qualitative and quantitative analysis according to testing result to organophosphorus ester based flame retardant；Wherein chromatographic condition is：
Gas chromatographic column：HP-701 14%Cyanopropyl Phenyl Methyl Capillary30.0m × 320 μm
×0.25μm；Carrier gas：High pure nitrogen；Input mode：Using Splitless injecting samples mode；Sample size：1 μ l, it is qualitative with retention time,
It is quantitative with sample peak area and standard comparing；Gas flow rate：Hydrogen：75ml/min, air：100ml/min, make-up gas (nitrogen
Gas)：15ml/min；Injector temperature：220℃；Detector (FPD) temperature：250℃；Column temperature program：120 DEG C of initial column temperature, it is permanent
Warm 2min；Then column temperature is increased to into 220 DEG C with the speed of 25 DEG C/min；Then, then with the speed of 5 DEG C/min by column temperature liter
Up to 260 DEG C.
Mass Spectrometry Conditions are：Ion source：EI(70eV)；Ion temperature：230℃；Quadrupole rod temperature：150℃；Interface temperature：
280℃；EM voltages：1165V；Acquisition mode：SIM；The solvent delay time：3.6min；Tuning manner：Automatically tuning；Full ion
Sweep limitss：50～500 μ.
(3) sample is detected again：Utilize31P-NMP is detected to solution to be measured, as a result with reference to the analysis result of step (2)
Further qualitative and quantitative analysis；
31P-NMP testing conditions are：D1 set of time is 50S, and sweep time is 10h, and solvent is deuterochloroform.
The phosphorus flame retardant for being detected is：PFR-A；Measured with internal standard method as internal standard substance using dibutyl phthalate
PFR-A contents in ABS plastic were 3.6% (PFR-A contains 10.6% in testing sample)；With deuterochloroform as solvent, core
Magnetic phosphorus spectrum chemical shift δ (ppm) be：12.01ppm.
Comparative example 2
The detection method of organophosphorus ester based flame retardant, comprises the following steps in a kind of detection ABS plastic：
(1) sample pretreatment：1.0g testing samples are accurately weighed, is crushed, then dissolved using tetrahydrofuran (10ml), in
Shaken at room temperature 1h, then vibration terminates, and with 0.5 μm of expanded microporous polytetra fluoroethylene-EPTEE Fibrous membrane filtration, obtains testing sample solution；
(2) sample detection：The organophosphorus ester based flame retardant in solution to be measured is examined using gas chromatograph-mass spectrometer
Survey, the then qualitative and quantitative analysis according to testing result to organophosphorus ester based flame retardant；Wherein chromatographic condition is：
Gas chromatographic column：HP-701 14%Cyanopropyl Phenyl Methyl Capillary30.0m × 320 μm
×0.25μm；Carrier gas：High pure nitrogen；Input mode：Using Splitless injecting samples mode；Sample size：1 μ l, it is qualitative with retention time,
It is quantitative with sample peak area and standard comparing；Gas flow rate：Hydrogen：75ml/min, air：100ml/min, make-up gas (nitrogen
Gas)：15ml/min；Injector temperature：220℃；Detector (FPD) temperature：250℃；Column temperature program：120 DEG C of initial column temperature, it is permanent
Warm 2min；Then column temperature is increased to into 220 DEG C with the speed of 25 DEG C/min；Then, then with the speed of 5 DEG C/min by column temperature liter
Up to 260 DEG C.
Mass Spectrometry Conditions are：Ion source：EI(70eV)；Ion temperature：230℃；Quadrupole rod temperature：150℃；Interface temperature：
280℃；EM voltages：1165V；Acquisition mode：SIM；The solvent delay time：3.6min；Tuning manner：Automatically tuning；Full ion
Sweep limitss：50～500 μ.
(3) sample is detected again：Utilize31P-NMP is detected to solution to be measured, as a result with reference to the analysis result of step (2)
Further qualitative and quantitative analysis；
31P-NMP testing conditions are：D1 set of time is 50S, and sweep time is 10h, and solvent is deuterochloroform.Detected
Phosphorus flame retardant be：PFR-B；PFR-B is measured in ABS plastic as internal standard substance internal standard method using dibutyl phthalate
Content is 2.5% (PFR-B has 7.1% in testing sample), with deuterochloroform as solvent, the chemical shift δ of nuclear-magnetism phosphorus spectrum
(ppm) it is：10.5ppm.
Comparative example 3
The detection method of organophosphorus ester based flame retardant, comprises the following steps in a kind of detection ABS plastic：
(1) sample pretreatment：1.0g testing samples are accurately weighed, is crushed, then dissolved using tetrahydrofuran (10ml), drop
Plus hydrolytic reagent shitosan cerium (IV) coordination compound acetum (0.2g/ml, 5ml), in shaken at room temperature 1h, then vibration terminates, uses
0.5 μm of expanded microporous polytetra fluoroethylene-EPTEE Fibrous membrane filtration, obtains testing sample solution；
(2) sample detection：The organophosphorus ester based flame retardant in solution to be measured is examined using gas chromatograph-mass spectrometer
Survey, it is then fire-retardant to determine corresponding organophosphorus compoundses according to the standard curve obtained in testing result and step (1)
The qualitative and quantitative analysis of agent；Wherein chromatographic condition is：
Gas chromatographic column：HP-701 14%Cyanopropyl Phenyl Methyl Capillary30.0m × 320 μm
×0.25μm；Carrier gas：High pure nitrogen；Input mode：Using Splitless injecting samples mode；Sample size：1 μ l, it is qualitative with retention time,
It is quantitative with sample peak area and standard comparing；Gas flow rate：Hydrogen：75ml/min, air：100ml/min, make-up gas (nitrogen
Gas)：15ml/min；Injector temperature：220℃；Detector (FPD) temperature：250℃；Column temperature program：120 DEG C of initial column temperature, it is permanent
Warm 2min；Then column temperature is increased to into 220 DEG C with the speed of 25 DEG C/min；Then, then with the speed of 5 DEG C/min by column temperature liter
Up to 260 DEG C.
Mass Spectrometry Conditions are：Ion source：EI(70eV)；Ion temperature：230℃；Quadrupole rod temperature：150℃；Interface temperature：
280℃；EM voltages：1165V；Acquisition mode：SIM；The solvent delay time：3.6min；Tuning manner：Automatically tuning；Full ion
Sweep limitss：50～500 μ.
(3) sample is detected again：Utilize31P-NMP is detected to solution to be measured, as a result with reference to the analysis result of step (2)
Further qualitative and quantitative analysis；
31P-NMP testing conditions are：D1 set of time is 50S, and sweep time is 10h, and solvent is deuterochloroform.Detected
Phosphorus flame retardant be：PFR-D；PFR-D is measured in ABS plastic as internal standard substance internal standard method using dibutyl phthalate
Content was 1.9% (PFR-D contains 5.6% in testing sample)；With deuterated dichloromethane as solvent, the chemical potential of nuclear-magnetism phosphorus spectrum
Moving δ (ppm) is：7.6ppm, 11.1ppm.
Comparative example 4
The detection method of organophosphorus ester based flame retardant, comprises the following steps in a kind of detection ABS plastic：
(1) sample pretreatment：1.0g testing samples are accurately weighed, is crushed, then dissolved using tetrahydrofuran (10ml), drop
Plus hydrolytic reagent shitosan cerium (IV) coordination compound acetum (0.2g/ml, 5ml), in shaken at room temperature 1h, then vibration terminates, uses
0.5 μm of expanded microporous polytetra fluoroethylene-EPTEE Fibrous membrane filtration, obtains testing sample solution；
(2) sample detection：The organophosphorus ester based flame retardant in solution to be measured is examined using gas chromatograph-mass spectrometer
Survey, it is then fire-retardant to determine corresponding organophosphorus compoundses according to the standard curve obtained in testing result and step (1)
The qualitative and quantitative analysis of agent；Wherein chromatographic condition is：
Gas chromatographic column：HP-701 14%Cyanopropyl Phenyl Methyl Capillary30.0m × 320 μm
×0.25μm；Carrier gas：High pure nitrogen；Input mode：Using Splitless injecting samples mode；Sample size：1 μ l, it is qualitative with retention time,
It is quantitative with sample peak area and standard comparing；Gas flow rate：Hydrogen：75ml/min, air：100ml/min, make-up gas (nitrogen
Gas)：15ml/min；Injector temperature：220℃；Detector (FPD) temperature：250℃；Column temperature program：120 DEG C of initial column temperature, it is permanent
Warm 2min；Then column temperature is increased to into 220 DEG C with the speed of 25 DEG C/min；Then, then with the speed of 5 DEG C/min by column temperature liter
Up to 260 DEG C.
Mass Spectrometry Conditions are：Ion source：EI(70eV)；Ion temperature：230℃；Quadrupole rod temperature：150℃；Interface temperature：
280℃；EM voltages：1165V；Acquisition mode：SIM；The solvent delay time：3.6min；Tuning manner：Automatically tuning；Full ion
Sweep limitss：50～500 μ.
(3) sample is detected again：Utilize31P-NMP is detected to solution to be measured, as a result with reference to the analysis result of step (2)
Further qualitative and quantitative analysis；
31P-NMP testing conditions are：D1 set of time is 50S, and sweep time is 10h, and solvent is deuterochloroform.Detected
Phosphorus flame retardant be：PFR-P；PFR-P is measured in ABS plastic as internal standard substance internal standard method using dibutyl phthalate
Content was 2.1% (PFR-P contains 6.1% in testing sample)；With deuterated dichloromethane as solvent, the chemical potential of nuclear-magnetism phosphorus spectrum
Moving δ (ppm) is：8.8ppm, 12.5ppm.
In sum, it is known that, the present invention a kind of detection ABS plastic in organophosphorus ester based flame retardant detection method with
Cracking is carried out without hydrolytic reagent to polymer to contrast, with good analytical effect, organophosphorus ester based flame retardant is carried
Beneficial detection method is supplied.
Above-mentioned example is merely illustrative, for explaining some features of the feature of the present invention.Appended claim
The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction, and the progress in science and technology will be formed due to language performance inaccurate reason and not
The possible equivalent or son being presently considered is replaced, and these changes also should be interpreted in the conceived case by appended
Claim is covered.
Claims (10)
1. it is a kind of detection ABS plastic in organophosphorus ester based flame retardant detection method, it is characterised in that at least including following step
Suddenly：
(1) sample pretreatment：Testing sample is accurately weighed, is crushed, dissolving adds hydrolytic reagent acetum, in shaken at room temperature 0.5
～2h, filters, and obtains testing sample solution；
(2) sample detection：Solution to be measured is detected using gas chromatograph-mass spectrometer, prepare liquid is carried out qualitative and quantitative
Preliminary analyses；
(3) sample is detected again：Utilize31P-NMP detects to solution to be measured, as a result enters one with reference to the analysis result of step (2)
The qualitative and quantitative analysis of step；
Wherein, hydrolytic reagent is shitosan cerium (IV) coordination compound.
2. the detection method of organophosphorus ester based flame retardant in ABS plastic is detected described in claim 1, it is characterised in that described
It is aminoacid alkaline earth compoundses that hydrolytic reagent also includes.
3. the detection method of organophosphorus ester based flame retardant in ABS plastic is detected described in claim 2, it is characterised in that described
Aminoacid alkaline earth compoundses are at least one or more in aminotriacetic acid magnesium complex, aminotriacetic acid calcium composition.
4. the detection method of organophosphorus ester based flame retardant in ABS plastic is detected described in claim 3, it is characterised in that described
Aminoacid alkaline earth compoundses are aminotriacetic acid calcium composition.
5. the detection method of organophosphorus ester based flame retardant in ABS plastic is detected described in claim 1, it is characterised in that described
Hydrolytic reagent is 1 with the mass ratio of acetum：(5～10).
6. the detection method of organophosphorus ester based flame retardant in ABS plastic is detected described in claim 1, it is characterised in that described
Hydrolytic reagent is 1 with the mass ratio of acetum：(5～8).
7. the detection method of organophosphorus ester based flame retardant in ABS plastic is detected described in claim 1, it is characterised in that described
Gas phase condition is：
Gas chromatographic column：HP-1701 14%Cyanopropyl Phenyl Methyl Capillary30.0m × 320 μ m
0.25μm；
Carrier gas：High pure nitrogen；
Input mode：Using Splitless injecting samples mode；
Sample size：1 μ l, it is qualitative with retention time, it is quantitative with sample peak area and standard comparing；
Gas flow rate：Hydrogen：75ml/min, air：100ml/min, make-up gas (nitrogen)：15ml/min；Injector temperature：
220℃；
Detector (FPD) temperature：250℃；
Column temperature program：100～120 DEG C of initial column temperature, constant temperature 2min；Then column temperature is increased to the speed of 20～30 DEG C/min
200～220 DEG C；Then, then with the speed of 1～6 DEG C/min column temperature is increased to into 240～280 DEG C.
8. the detection method of organophosphorus ester based flame retardant in ABS plastic is detected described in claim 1, it is characterised in that described
Mass Spectrometry Conditions are：
Ion source：EI(70eV)；
Ion temperature：230℃；
Quadrupole rod temperature：150℃；
Interface temperature：280℃；
EM voltages：1165V；
Acquisition mode：SIM；
The solvent delay time：3～4min；
Tuning manner：Automatically tuning；
Full ion scan scope：50～500 μ.
9. the detection method of organophosphorus ester based flame retardant in ABS plastic is detected described in claim 7, it is characterised in that described
Column temperature program：120 DEG C of initial column temperature, constant temperature 2min；Then column temperature is increased to into 220 DEG C with the speed of 25 DEG C/min；Then, so
Afterwards column temperature is increased to into 260 DEG C with the speed of 5 DEG C/min.
10. the detection method of organophosphorus ester based flame retardant in ABS plastic is detected described in claim 1, it is characterised in that institute
State31P-NMP test conditions are as follows：D1 set of time is 30～60S, and sweep time is 4～12h, and solvent is deuterochloroform.
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| CN109668981A (en) * | 2018-12-25 | 2019-04-23 | 广东省东莞市质量监督检测中心 | A kind of method of phosphor-containing flame-proof agent content and the amount of migration in measurement toy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103616469A (en) * | 2013-12-13 | 2014-03-05 | 中华人民共和国北京出入境检验检疫局 | Method for detecting organophosphate flame retardant |
| CN105067723A (en) * | 2015-09-30 | 2015-11-18 | 同济大学 | Gas chromatography-tandem quadrupole mass spectrometry analysis method of soil / sediment organophosphate flame retardant |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103616469A (en) * | 2013-12-13 | 2014-03-05 | 中华人民共和国北京出入境检验检疫局 | Method for detecting organophosphate flame retardant |
| CN105067723A (en) * | 2015-09-30 | 2015-11-18 | 同济大学 | Gas chromatography-tandem quadrupole mass spectrometry analysis method of soil / sediment organophosphate flame retardant |
Non-Patent Citations (3)
| Title |
|---|
| 张晓娟 等: "壳聚糖金属配合物对冬枣保鲜作用及降解有机磷农药", 《农业工程学报》 * |
| 班大明 等: "聚苯氧基磷酸对苯二酚酯的合成、表征及其热稳定性研究", 《功能材料》 * |
| 耿娟: "氨基酸碱土金属配合物的合成、结构表征及对磷酸酯键的水解作用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
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|---|---|---|---|---|
| CN109668981A (en) * | 2018-12-25 | 2019-04-23 | 广东省东莞市质量监督检测中心 | A kind of method of phosphor-containing flame-proof agent content and the amount of migration in measurement toy |
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