CN104359997B - Head space-GC-MS is measured the method for the low boiling halogenated hydrocarbons in solvent-borne type woodwork coating - Google Patents
Head space-GC-MS is measured the method for the low boiling halogenated hydrocarbons in solvent-borne type woodwork coating Download PDFInfo
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Abstract
The invention belongs to halogenated hydrocarbons detection technique field, specifically disclose the method for the low boiling halogenated hydrocarbons in head space-GC-MS mensuration solvent-borne type woodwork coating. The present invention is carrying out, before headspace sampling, treated testing sample supernatant is coated with to processing at head space bottle inwall, and this operation ensures in head space bottle that sample completes gasification within a short period of time; Coordinate gas-chromatography can well halogenated hydrocarbons and other components effectively be separated to identification with mass spectrograph, thereby can measure halogenated hydrocarbons content separately. Under the detection of single halogenated hydrocarbons, be limited to 0.005%, the measured object rate of recovery 90%～105%, linear dependence 0.9993 ~ 0.9997, the relative deviation of twice measurement result of same operator is less than 5%, and between different experiments chamber, the relative mistake of test result is less than 10%. The method is highly sensitive, the degree of accuracy is high, specificity is strong, simple to operate, highly versatile; There is applicability and realistic meaning widely, be applicable to the conventional quality control of the low boiling halogenated hydrocarbons in solvent-borne type woodwork coating.
Description
Technical field
The present invention relates to halogenated hydrocarbons detection technique field, more specifically, relate to head space-GC-MS and measure solventThe method of the low boiling halogenated hydrocarbons in type woodwork coating.
Background technology
Coating is the second largest emission source of VOC, and halogenated hydrocarbons also belongs to the great volatility of bio-toxicityOrganic compound, existing to the standard GB/T 18581-2009 " indoor decorating and refurnishing materials that adopt of halogenated hydrocarbons mensuration in coating moreLimits of harmful substances standard in solvent-borne type woodwork coating ", in this standard, the halogenated hydrocarbons in solvent-borne type woodwork coating is specified to gasThe detection method of phase chromatogram electron capture detector, the method adopts internal standard method, but in actual detection, finds such detectionMethod exists some not enough: (1) electron capture detector can only have response to electronegativity material, but cannot differentiate corresponding reservation timeBetween chromatographic peak whether be our object, easily cause the false positive of testing result; (2) requirement of internal standard method is internal standard compoundWith the response of object to be measured should be at the same order of magnitude, and for using electron capture detector to measure halogenated hydrocarbon material, the number difference of the halogen that object molecule contains can cause response to have the difference of geometric progression, obviously weBe difficult to find a kind of suitable internal standard compound to meet the basically identical requirement of this response simultaneously; (3) sample before sampling byConstruction ratio is mixed, and in operation, easily causes sample homogeneity deficiency, also easy steam dilution solvent while mixing each componentVolatilization, further cause sampling to lack representative, this point also seems for the polyurethanes coating that need to use curing agentPolymerization is more not easy to determine, because curing agent, in the time of married operation, will occur; (4) liquid after Paint dilution dissolvingSample introduction, can cause the residual more nonvolatile matter at injection port place, and these materials can cause absorption to subsequent sample, and then cause sampleThe repeatability that product detect is not good enough.
In prior art, also there are much detection techniques for halogenated hydrocarbons: Zhang Weiya etc. have studied headspace sampling gas chromatography mass spectrometryMethod is measured in coating 12 kinds of halogenated hydrocarbons and benzene homologues; Xue Ximei etc. have studied the gas phase look of 16 kinds of harmful substances in solvent based coatingSpectrum-mass spectrum Simultaneous Detection. Although have the relevant report that in above-mentioned coating, halogenated hydrocarbons detects in prior art, solvent-borne type woodDevice coating is divided into again multiple, is divided into polyurethane woodware coating, nitrocellulose woodenware coating, formaldehyde alkyd woodenware painting according to resinous type usedMaterial, phenolic aldehyde woodwork coating and acid cure alkyd amino woodwork coating, but for each coating, the content of its contained halogenated hydrocarbonsBe not quite similar with kind, therefore in carrying out variety classes coating with head space-GC-MS, when the detection of halogenated hydrocarbons, haveNecessary specific aim is adjusted optimization, thereby the operability of the method is strengthened, and measurement accuracy improves.
Summary of the invention
Technical problem to be solved by this invention is to overcome head space-gas chromatographic detection solvent-borne type woodenware in prior art to be coated withThe existing technological deficiency of halogenated hydrocarbons in material, provides a kind of headspace sampling method of solvent-borne type woodwork coating sample.
Another object of the present invention be to provide a kind of highly sensitive, specificity is strong, simple to operate, highly versatile, be suitable forLow boiling halogenated hydrocarbons (carrene, 1,1-dichloroethanes, chloroform, 1,1,1-trichlorine in the wide solvent based coating of propertyEthane, 1,2-dichloroethanes, carbon tetrachloride, trichloro-ethylene, 1,1,2-trichloroethanes) detection method.
The 3rd object of the present invention is to provide a kind of method of solvent-borne type woodwork coating sample pre-treatments.
Object of the present invention is achieved by the following technical programs:
A headspace sampling method for solvent-borne type woodwork coating, by treated coating sample leave standstill, get supernatant inIn head space bottle, auxiliary by gravity flow or the instrument of supernatant, make it be evenly distributed on head space bottle inwall, remove unnecessary supernatant,Sealing head space bottle detects for head space.
Carrying out before headspace sampling, need preparation to meet the compo sample of sample marker construction ratio. Preferably, be coated withThe preparation method of material sample is: get diluent that certain volume is suitable in being with graduated colorimetric cylinder, comply with according to construction ratioThe inferior each component of coating to be measured that takes mixes coating under the state that has retarder thinner to exist.
Preferably, above-mentioned headspace sampling method is: get a certain amount of treated coating sample and leave standstill, get supernatant in knownQuality, in certain specification head space bottle, auxiliary by gravity flow or the spreading implement of sample supernatant, sample supernatant is evenly dividedCloth is at head space bottle inwall. After being coated with, sample supernatant unnecessary at the bottom of head space bottle is discharged by bottleneck, bottleneck absorbent cotton wipingAfter clean, again weigh, ensure head space bottle inwall sample supernatant coating film forming, detect for head space with the good sample bottle of rear enclosed.
More preferably, described in the time that coating sample is carried out to dilution process, diluent is one in butyl acetate, cyclohexanonePlant or two kinds; Described curing agent is the conventional curing agent in this area, as toluene di-isocyanate(TDI) TDI, hexa-methylene isocyanatesThe prepolymer of HDI or methyl diphenylene diisocyanate MDI. Described host is film forming matter and a small amount of retarder thinner, has colorBe mixed with metal or organic toner.
The preparation method of above-mentioned treated coating sample is: get the diluent of certain volume in being with graduated colorimetric cylinderIn, take successively curing agent and/or retarder thinner and coating according to construction ratio, on eddy mixer, mix, only putAfter a period of time, get supernatant to be analyzed, described retarder thinner is Tianna solution or banana oil.
Preparation how to carry out sample with adopt which kind of effective sample injection method by consistent approval for be gas-chromatography successfullyThe key factor of analyzing, the present invention is in order to reach the object of the halogenated hydrocarbons in accurate and sensitive detection coating, to coating to be measuredSample has carried out improvement sampling mode, is first how to obtain reappearing and representative detecting for headspace gasCoating sample, for coating sample, often can adopt suitable diluent to dilute to facilitate detection to it in prior art, and it is conventionalDiluent have silicone oil, acetonitrile, ethyl acetate etc., but for different types of coating, need to select different diluents, dilutionWhether fully agent solubilized target coating has considerable influence to analyzing and testing result, the present invention is directed to different coating, by coatingMix from different diluents, to obtain preferably disperse dilution effect for analyzing and testing coating sample.
Secondly also need to do a lot of considerations for the sample injection method of coating sample, because of the character of coating itself, make its districtNot, in general fixing or liquid substance, in the time carrying out headspace sampling, do not need significant care, in prior art for coating sampleAlso as conventional sample, get a certain amount of head space bottle just start afterwards detect analyze, this operation not only makes in thing to be detected by gasThe content of changing tails off, and also can increase detection time and testing cost, cause testing result deviation larger, and the present invention is in existing skillOn the basis of art, optimize the flow process of sampling, made that sampling operation is more easy rationally, institute sample thief also has better representativeProperty; Consider ductility and the coating of coating sample simultaneously, be coated with after coating sample is added to head space bottle, make coatingSample is dispersed in head space bottle, and this coating operation is conducive to the release of volatile organic matter in head space bottle in sample,Make testing result more accurate.
Provide head space-GC-MS to measure the method for the low boiling halogenated hydrocarbons in solvent-borne type woodwork coating, compriseFollowing steps:
S1. sample pretreating: get the diluent of certain volume in colorimetric cylinder, take successively painting to be measured according to construction ratioExpect each component and mix;
S2. headspace sampling: the mixture that S1 is obtained leaves standstill, and gets supernatant in head space bottle, by sample supernatantGravity flow or instrument are auxiliary, make sample supernatant be evenly distributed on head space bottle inwall, remove unnecessary sample supernatant sealing head space bottle;
S3. sample determination: adopt head space-GC-MS, wherein:
Head space condition is: 80～120 DEG C of head space equilibrium temperatures, balance 10～20min, 100～125 DEG C of sampling probes, transmissionLine temperature is 120～135 DEG C;
GC conditions is: chromatographic column is 5% phenyl/95% methylsiloxane capillary column, 30m × 0.25mm × 0.25μ m, post case adopts temperature programming; 30 DEG C of maintenance 12min of initial temperature, then be warming up to 150 DEG C of maintenance 2min, 30 with 10 DEG C/minDEG C/min be warming up to 180 DEG C keep 1min; Input mode is split sampling, and split ratio is 1～2:1, injector temperature 120～150 DEG C; Sample injection time 1.5min; Carrier gas is high-purity helium; The quantitatively long-pending 1ml of ring body; Flow rate of carrier gas: 10～20ml/min;
Mass spectrum condition is: ionization mode is electron impact ionization source, and bombardment ability is 70eV; 230 DEG C of ion source temperatures; Four150 DEG C of level bar temperature; 250 DEG C of GC-MS interface temperature; Detecting pattern is for selecting ion monitoring.
Preferably, step S1 gets diluent that certain volume is suitable in being with graduated colorimetric cylinder, according to construction ratioExample takes the each component of coating to be measured successively, again weighs after being settled to scale, on eddy mixer, mixes; This operationCan make the time that the each component of coating exposes in air shorten as far as possible, guarantee the representativeness of institute's sample thief, also reducing can be mutualThe speed that the component of polymerization is reacted.
When above-mentioned detection, sample headspace bottle, after heating, volatilizes retarder thinner and halogenated hydrocarbons, the testing sample after gasificationEnter in gas chromatograph with inert carrier gas, after chromatographic column separates, measure with mass spectrograph, to select ion quantitative. Every kind of haloHydrocarbon is selected 3 qualitative ions, wherein comprises a quota ion.
Preferably, S1 is specially the diluent of getting certain volume amount in being with graduated colorimetric cylinder, according to construction ratioTake successively each components such as coating to be measured, again weigh after being settled to scale, on eddy mixer, mix.
Preferably, S2 is specially the 20ml specification head space bottle of getting a certain amount of S1 mixture supernatant and be placed in known qualityIn, auxiliary by gravity flow or the spreading implement of sample supernatant, make sample supernatant be evenly distributed on head space bottle inwall. Be coated withCheng Hou, sample supernatant unnecessary at the bottom of head space bottle is discharged by bottleneck, and bottleneck, with again weighing after absorbent cotton wiped clean, seals subsequentlyClose sample bottle.
The present invention uses the carrene, 1 of concentration known, 1-dichloroethanes, chloroform, 1,1,1-tri-chloroethenesAlkane, 1,2-dichloroethanes, carbon tetrachloride, trichloro-ethylene, 1,1,2-trichloroethanes standard mixed solution, according to above-mentioned sample topEmpty sample introduction program, is introduced into gas chromatograph-mass spectrometer, records the retention time of test compound, by contrasting tested chemical combinationThe standard retention time of thing and characteristic ion abundance recently determine whether to have this compound, then drawing standard curve negotiating is selectedIon carries out quantitatively.
It should be noted that, adopt said method of the present invention can measure any one low boiling halogenated hydrocarbons.
For different types of coating, the detected parameters in its detection method, as selected diluent, head space balance temperatureDegree, equilibration time etc. influence each other, final decision testing result significant difference, concrete for polyurethane coating, its detectionParameter can reference example 1, and for nitro paint, its detected parameters can reference example 2, to alkyd paint, and its detectionParameter can reference example 3.
Compared with prior art, beneficial effect of the present invention:
First the present invention provides a kind of method for making sample of coating sample, takes successively coating to be measured according to construction ratioEach component in adding the scale colorimetric cylinder of diluent, avoided that GB explains mix sample operation time, must followThe uniformity that causes of solvent evaporates and repeat sample preparation and cannot ensure conforming defect; Select butyl acetate and cyclohexanone to beDiluent, the chromatographic peak of butyl acetate, cyclohexanone separates good with each target peak, thereby avoids the wider solvent peak of appearance timeInterference; The present invention was coated with processing by testing sample at head space bottle inwall before carrying out head space-gas-chromatography, this behaviourThe method of doing has effectively been improved sample volatilization condition in head space bottle, ensures that in head space bottle, sample completes gasification within a short period of time, changesKind common vapor liquid equilibrium head space method needs stable deficiency of long period; Adopt headspace sampling, can avoid moisture content, high boiling product orNonvolatile matter causes overload and pollution problem to analytical column, is also conducive to reduce the maintenance of gas chromatograph-mass spectrometer and makeUse cost. The present invention can well effectively separate identification by halogenated hydrocarbons and other components, thereby can measure halogenated hydrocarbons separatelyContent. Under the detection of single halogenated hydrocarbons, be limited to 0.005%, the measured object rate of recovery 90%～105%, linear dependence 0.9993 ~0.9997, the relative deviation of twice measurement result of same operator is less than 5%, and between different experiments chamber, the relative mistake of test result is littleIn 10%. In this invention, halogenated hydrocarbons detection collection of illustrative plates false positive can clearly be judged simultaneously, and sample detection is reproducible, selects ion fixedAmount is accurate, head space-gas chromatography mass spectrometer highly versatile, and therefore this invention has applicability and realistic meaning widely.
Brief description of the drawings
Fig. 1 is carrene, 1,1-dichloroethanes, chloroform, 1,1, and 1-trichloroethanes, 1,2-dichloroethanes,Carbon tetrachloride, trichloro-ethylene, 1,1, the total ion current figure of 2-trichloroethanes standard mixed solution; Chromatographic peak order from left to rightBe followed successively by carrene, 1,1-dichloroethanes, chloroform, 1,1,1-trichloroethanes, 1,2-dichloroethanes, tetrachloroCarbon, trichloro-ethylene, 1,1,2-trichloroethanes;
Fig. 2 is that different disposal sample records 1,1-dichloroethanes content and head space equilibration time tendency chart described in embodiment 1,Wherein abscissa is equilibration time, the min of unit; Ordinate is test result content, the % of unit;
Fig. 3 is that different disposal sample records carrene content and head space equilibration time tendency chart described in embodiment 2; ItsIn, abscissa is equilibration time, the min of unit; Ordinate is test result content, the % of unit.
Detailed description of the invention
Below by Figure of description and specific embodiment, the present invention is further specifically described. Design philosophy of the present inventionOr simple the substituting of allied substances belongs to protection scope of the present invention. If following used experimental technique is without specified otherwise, allFor the method for the existing routine of the art, the batching using or material, if no special instructions, being can by commercial sourcesThe batching obtaining or material.
The mensuration of halogenated hydrocarbons in embodiment 1 polyurethane coating
Sample construction ratio is host (main paint): curing agent (TDI): retarder thinner (Tianna solution)=1:0.5:0.5(qualityThan). Get 25ml color-comparison tube, add about 5g(to be accurate to 0.1mg, lower same) butyl acetate, take successively master according to construction ratioThe each component of paint, TDI and Tianna solution, amounts to 5g sample. Mixture mixes with eddy mixer and leaves standstill, and gets supernatant turn with suction pipeMove in clean 20ml specification head space bottle, make the gravity flow of sample supernatant be applied to head space bottle inwall by rotation head space bottle, manyRemaining sample supernatant is discharged by bottleneck, sealing top empty bottle immediately. The of poor quality of head space bottle coating front and back is secondary sample quality0.2g(is defined as 1# sample), directly get the above-mentioned sample 0.1g(2# sample that mixes), 0.5g(3# sample), 1.0g(4# sample) be placed in head space bottleThe end, according to GB18581-2009 Appendix B test specimens (5# sample). The equal parallel testing twice of above-mentioned test specimens, calculating mean value is with inclined to one sidePoor.
By the head space bottle making, for head space-gaschromatographic mass spectrometry, head space-gas chromatography mass spectrometer condition of work is as follows:
(a) 80 DEG C of head space equilibrium temperatures, balance 10min, 20min, 30min, 40min, 50min, 60min successively, sampling100 DEG C, pin, transmission line temperature is 120 DEG C, carrier gas is high-purity helium; The quantitatively long-pending 1ml of ring body; Flow rate of carrier gas 20ml/min.
(b) 120 DEG C of gas chromatographic sample introduction mouth temperature; Sample injection time 1.5min; Split ratio 1:1.
(c) chromatographic column: the capillary chromatographic column of 30m × 0.25mm × 0.25 μ m, 5% phenyl/95% methylsiloxane capillaryPost; Carrier gas flux 1.00ml/min(constant flow rate).
(d) column temperature: 30 DEG C of maintenance 12min of initial temperature, then be warming up to 150 DEG C of maintenance 2min with 10 DEG C/min, 30 DEG C/Min is warming up to 180 DEG C and keeps 1min.
(e) electron impact ionization source: 70eV.
(f) ion source temperature: 230 DEG C.
(g) level Four bar temperature: 150 DEG C.
(h) GC-MS interface temperature: 250 DEG C.
(i) select ion detection: every kind of halogenated hydrocarbons is selected 3 qualitative ions, wherein comprises a quota ion, halogenated hydrocarbonsMonitoring ion includes but not limited to chemical combination described in table 1 referring to object-low boiling halogenated hydrocarbons of table 1(detection of the present inventionThing).
By with halogenated hydrocarbons standard appearance time and characteristic ion abundance ratio, determine in sample, contain 1,1-dichloroethanes,Trichloro-ethylene, according to target ion calculated by peak area of employing external standard method, records 1,1-dichloroethanes content and head space equilibration time becomesGesture is as Fig. 2, and result shows that the coating operation of 1# sample has obviously excellent for shortening head space equilibration time, raising analytical test efficiencyGesture. Table 2 all reaches the parallel testing result table of comparisons after equilibration time for each test specimens, also can be found out the head space of 1# by table 2In bottle, coating test specimens has good reappearance, and has less standard deviation.
The mensuration of halogenated hydrocarbons in embodiment 2 nitro paints
Sample construction ratio is host: retarder thinner=1:0.2(mass ratio). Get 25ml color-comparison tube, add 5.0g ringHexanone, takes alkyd resins (host) and Tianna solution (retarder thinner) successively according to construction ratio, amounts to 5.0g sample. Mixture is usedEddy mixer mixes and leaves standstill, and sample supernatant is transferred in clean 20ml specification head space bottle with suction pipe, by rotationHead space bottle makes the gravity flow of sample supernatant be applied to head space bottle inwall, and unnecessary sample supernatant is discharged by bottleneck, seals subsequently head spaceBottle. Of poor quality before and after head space bottle coating is secondary sample quality 0.2g(1# sample), directly get the above-mentioned sample 0.1g(2# sample that mixes),0.5g(3# sample), 1.0g(4# sample) be placed in head space bottle at the bottom of, according to GB18581-2009 Appendix B test specimens (5# sample). Above-mentioned testSample equal parallel testing twice, calculating mean value and deviation.
By the head space bottle making, for head space-gaschromatographic mass spectrometry, head space-gas chromatography mass spectrometer condition of work is as follows:
(a) 100 DEG C of head space equilibrium temperatures, balance 10min, 20min, 30min, 40min, 50min, 60min successively, sampling110 DEG C, pin, transmission line temperature is 120 DEG C, carrier gas is high-purity helium; The quantitatively long-pending 1ml of ring body; Flow rate of carrier gas 20ml/min.
(b) 120 DEG C of gas chromatographic sample introduction mouth temperature; Sample injection time 1.5min; Split ratio 2:1.
(c) chromatographic column: the capillary chromatographic column of 30m × 0.25mm × 0.25 μ m, 5% phenyl/95% methylsiloxane capillaryPost; Carrier gas flux: 1.00ml/min(constant flow rate).
(d) column temperature: 30 DEG C of maintenance 12min of initial temperature, then be warming up to 150 DEG C of maintenance 2min with 10 DEG C/min, 30 DEG C/Min is warming up to 180 DEG C and keeps 1min.
(e) electron impact ionization source: 70eV.
(f) ion source temperature: 230 DEG C.
(g) level Four bar temperature: 150 DEG C.
(h) GC-MS interface temperature: 250 DEG C.
(i) select ion detection: every kind of halogenated hydrocarbons is selected 3 qualitative ions, wherein comprises a quota ion, halogenated hydrocarbonsMonitoring ion includes but not limited to chemical combination described in table 1 referring to object-low boiling halogenated hydrocarbons of table 1(detection of the present inventionThing).
By with halogenated hydrocarbons standard appearance time and characteristic ion abundance ratio, determine and in sample, contain carrene, 1,1,2-trichloroethanes, adopts according to target ion calculated by peak area of external standard method, records carrene content and head space equilibration time trendAs Fig. 3, result shows that the coating operation of 1# sample has a clear superiority in for shortening head space equilibration time, raising analytical test efficiency.
Table 3 for each test specimens all reach parallel testing result after equilibration time with according to GB18581-2009 Appendix B sideThe method test result table of comparisons, same, in the head space bottle of 1#, coating test specimens has good reappearance, and has less standardDeviation.
The mensuration of halogenated hydrocarbons in embodiment 3 alkyd paints
Sample construction ratio is host: retarder thinner=1:0.5. Get 25ml color-comparison tube, add 5.0g volume ratio 1:1Butyl acetate cyclohexanone mixed solvent, take successively alkyd resins (host) and banana oil (retarder thinner) according to construction ratio,Amount to 5g sample. Mixture mixes with eddy mixer and leaves standstill, and with suction pipe, sample supernatant is transferred to clean 20ml and advisesIn lattice head space bottle, make the gravity flow of sample supernatant be applied to head space bottle inwall by rotation head space bottle, unnecessary sample supernatant is by bottleMouth is discharged, sealing top empty bottle subsequently. The of poor quality of head space bottle coating front and back is secondary sample quality 0.2g, parallel test six times,Calculating mean value and RSD, be defined as S test specimens. Carry out contrast test according to GB18581-2009 Appendix B method of testing simultaneously:A sample, test after mixing sample gross weight 5g according to construction ratio; B sample, test after mixing sample gross weight 10g according to construction ratio; CSample, test after mixing sample gross weight 20g according to construction ratio; D sample, test after mixing sample gross weight 30g according to construction ratio; ESample, test after mixing sample gross weight 40g according to construction ratio;
By the head space bottle making, for head space-gaschromatographic mass spectrometry, head space-gas chromatography mass spectrometer condition of work is as follows:
(a) 120 DEG C of head space equilibrium temperatures, balance 15min, 125 DEG C of sampling probes, transmission line temperature is 135 DEG C, carrier gas is highPure helium; The quantitatively long-pending 1ml of ring body; Flow rate of carrier gas 15ml/min.
(b) 150 DEG C of gas chromatographic sample introduction mouth temperature; Sample injection time 1.5min, split ratio 1:1.
(c) chromatographic column: the capillary chromatographic column of 30m × 0.25mm × 0.25 μ m, 5% phenyl/95% methylsiloxane capillaryPost; Carrier gas flux: 1.00ml/min(constant flow rate).
(d) column temperature: 30 DEG C of maintenance 12min of initial temperature, then be warming up to 150 DEG C of maintenance 2min with 10 DEG C/min, 30 DEG C/Min is warming up to 180 DEG C and keeps 1min.
(e) electron impact ionization source: 70eV.
(f) ion source temperature: 230 DEG C.
(g) level Four bar temperature: 150 DEG C.
(h) GC-MS interface temperature: 250 DEG C.
(i) select ion detection: every kind of halogenated hydrocarbons is selected 3 qualitative ions, wherein comprises a quota ion, halogenated hydrocarbonsMonitoring ion includes but not limited to chemical combination described in table 1 referring to object-low boiling halogenated hydrocarbons of table 1(detection of the present inventionThing).
By with halogenated hydrocarbons standard appearance time and characteristic ion abundance ratio, determine three chloromethanes that contain 0.057% in sampleAlkane and 0.025% 1,1,1-trichloroethanes, adopts external standard method according to target ion calculated by peak area, the knot of chloroform testReally, mean value and RSD value are as table 4.
Result show, in target retarder thinner according to construction ratio add successively each component S test specimens test valueHeight, and there is less RSD value, parallel determination favorable reproducibility is described; And in the survey according to GB18581-2009 Appendix B methodIn examination, the sample mixing on a small quantity has larger uncertainty in the time of retest, and the impact that diluent volatilization etc. brings is brighterAobvious, the sample size only mixing in increasing and complete within the utmost point short time and mix and sample operation and could reduce to a certain extent thisPlant uncertainty, this can cause the workload increasing of experiment and the reduction of efficiency, increases testing cost and burden.
Claims (4)
1. a headspace sampling method for solvent-borne type woodwork coating, is characterized in that,
Get a certain amount of treated coating sample and leave standstill, get supernatant in head space bottle, by gravity flow or the painting of sample supernatantCloth instrument is auxiliary, makes sample supernatant be evenly distributed on head space bottle inwall, after being coated with, and unnecessary sample supernatant at the bottom of head space bottleLiquid is discharged by bottleneck, and bottleneck, with again weighing after absorbent cotton wiped clean, ensures head space bottle inwall sample supernatant coating film forming,Detect for head space with the good sample bottle of rear enclosed.
2. headspace sampling method according to claim 1, is characterized in that, the processing method of described coating sample is, getsThe diluent of certain volume, in colorimetric cylinder, takes successively the each component of coating to be measured and mixes according to construction ratio.
3. headspace sampling method according to claim 2, is characterized in that, described diluent is butyl acetate, cyclohexanoneIn one or both.
4. head space-GC-MS is measured the method for the low boiling halogenated hydrocarbons in solvent-borne type woodwork coating, it is characterized in that,Comprise the following steps:
S1. sample pretreating: get the diluent of certain volume in colorimetric cylinder, take successively coating to be measured according to construction ratio eachComponent also mixes;
S2. headspace sampling: the mixture that S1 is obtained leaves standstill, and gets supernatant in head space bottle, by the gravity flow of sample supernatantOr instrument is auxiliary, makes sample supernatant be evenly distributed on head space bottle inwall, remove unnecessary sample supernatant sealing head space bottle;
S3. adopt head space-GC-MS to detect being arranged in sealing head space bottle sample supernatant.
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| CN108008025A (en) * | 2017-10-23 | 2018-05-08 | 广东省东莞市质量监督检测中心 | Method that is a kind of while detecting a variety of volatile organic matters in marking pen |
| CN107703247A (en) * | 2017-10-23 | 2018-02-16 | 广东省东莞市质量监督检测中心 | Method that is a kind of while detecting volatile organic matter in coating |
| CN111007182B (en) * | 2019-12-30 | 2022-03-25 | 山东华安新材料有限公司 | Method for determining impurities in 2, 2-difluoroethanol by gas chromatography |
| CN111537636A (en) * | 2020-05-11 | 2020-08-14 | 苏州苏水环境监测服务有限公司 | Determination of four haloacetonitrile in water by headspace capillary gas chromatography |
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