CN104359997A - Method for measuring low-boiling-point halogenated hydrocarbon in solvent-based wood coating with headspace gas chromatography-mass spectrometry - Google Patents
Method for measuring low-boiling-point halogenated hydrocarbon in solvent-based wood coating with headspace gas chromatography-mass spectrometry Download PDFInfo
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Abstract
The invention belongs to the technical field of halogenated hydrocarbon detection, and particularly discloses a method for measuring low-boiling-point halogenated hydrocarbon in a solvent-based wood coating with the headspace gas chromatography-mass spectrometry. According to the method, the supernatant of a processed to-be-measured sample is subjected to coating treatment on the inner wall of a headspace bottle before headspace sampling, and the sample in the headspace bottle finishes gasification in shorter time through the operation; through matching of a gas chromatography-mass spectrometer, halogenated hydrocarbon and other components can be effectively separated and recognized very well, and respective content of halogenated hydrocarbon can be measured; and the lower limit of detection of single halogenated hydrocarbon is 0.005%, the analyte recovery rate is 90%-105%, the linear dependence is 0.9993-0.9997, the relative deviation of two times of measuring results obtained by the same operator is smaller than 5%, and the relative difference of measurement results in different laboratories is smaller than 10%. The method is high in sensitivity, accuracy, specificity and universality and simple to operate, has wide applicability and practical significance and is suitable for general quality control of low-boiling-point halogenated hydrocarbon in the solvent-based wood coating.
Description
Technical field
The present invention relates to halogenated hydrocarbons detection technique field, more specifically, relate to the method for the low boiling halogenated hydrocarbons in HS GC mass spectrometric determination solvent wood coatings.
Background technology
Coating is the second largest emission source of volatile organic compounds, halogenated hydrocarbons also belongs to the great volatile organic compounds of bio-toxicity, existing to halogenated hydrocarbons mensuration many employings standard GB/T 18581-2009 " in indoor decorating and refurnishing materials solvent wood coatings limits of harmful substances standard " in coating, in this standard, the halogenated hydrocarbons in solvent wood coatings is defined to the detection method of gas chromatography electron capture detector, the method adopts internal standard method, but find in actual detection, there is some deficiency in such detection method: (1) electron capture detector can only have response to electronegativity material, whether the chromatographic peak but cannot differentiating corresponding retention time is our object, easily cause the false positive of testing result, (2) requirement of internal standard method is that the response of internal standard compound and object to be measured should at the same order of magnitude, and halogenated hydrocarbon material is measured for use electron capture detector, the number difference of the halogen that target molecule contains can cause response to have the difference of geometric series, and obviously we are difficult to find a kind of suitable internal standard compound to meet the basically identical requirement of this response simultaneously, (3) sample mixes in construction ratio before sampling, operationally easily cause sample homogeneity not enough, the volatilization of also easy steam dilution solvent when mixing each component, sampling is caused to lack further representative, this point is not easy to determine, because hardening agent polymerization will occur when married operation for needing to use the polyurethanes coating of hardening agent also to seem more, (4) Liquid sample introduction after Paint dilution dissolving, can cause remaining more nonvolatile matter at injection port place, these materials can cause absorption to subsequent sample, and then cause the repeatability of sample detection not good enough.
Also have in prior art and much 12 kinds of halogenated hydrocarbons and benzene homologues in headspace sampling gas chromatography mass spectrometry method mensuration coating be have studied for the detection technique of halogenated hydrocarbons: Zhang Weiya etc.; Xue Ximei etc. have studied the gas chromatography-mass spectrum Simultaneous Detection of 16 kinds of objectionable impuritiess in solvent based coating.Although there is the relevant report that in above-mentioned coating, halogenated hydrocarbons detects in prior art, but solvent wood coatings is divided into again multiple, polyurethane woodware coating is divided into according to resinous type used, nitrocellulose woodenware coating, formaldehyde alkyd woodenware coating, phenolic aldehyde woodwork coating and acid cure alkyd amino woodwork coating, but for each coating, content and the kind of the halogenated hydrocarbons contained by it are not quite similar, therefore when carrying out the detection of halogenated hydrocarbons in variety classes coating by HS GC mass spectroscopy, be necessary that specific aim carries out adjusting and optimizing, thus the operability of the method is strengthened, measurement accuracy improves.
Summary of the invention
Technical matters to be solved by this invention overcomes HS GC in prior art to detect the technological deficiency in solvent wood coatings existing for halogenated hydrocarbons, provides a kind of headspace sampling method of solvent wood coatings sample.
Another object of the present invention is to provide low boiling halogenated hydrocarbons (methylene chloride, 1 in a kind of highly sensitive, specificity is strong, simple to operate, highly versatile, applicability are wide solvent based coating, 1-ethylene dichloride, methenyl choloride, 1,1,1-trichloroethanes, 1,2-ethylene dichloride, phenixin, triclene, 1,1,2-trichloroethanes) detection method.
3rd object of the present invention is to provide a kind of method of solvent wood coatings sample pre-treatments.
Object of the present invention is achieved by the following technical programs:
A headspace sampling method for solvent wood coatings, leaves standstill by treated coating sample, gets supernatant in ml headspace bottle, assisted by the gravity flow of supernatant or instrument, make it be evenly distributed on ml headspace bottle inwall, remove unnecessary supernatant, close ml headspace bottle and be used for head space detection.
Before carrying out headspace sampling, preparation is needed to meet the compo sample of sample marker construction ratio.Preferably, the preparation method of coating sample is: get the suitable thinning agent of certain volume in the graduated color comparison tube of band, taking each component of coating to be measured successively, mixing coating under the state existed there being diluting solvent according to construction ratio.
Preferably, above-mentioned headspace sampling method is: get a certain amount of treated coating sample and leave standstill, get supernatant in known quality, in certain specification ml headspace bottle, assisted by the gravity flow of sample supernatant or spreading implement, make sample supernatant be evenly distributed on ml headspace bottle inwall.After being coated with, sample supernatant unnecessary at the bottom of ml headspace bottle is discharged by bottleneck, again weighs after bottleneck absorbent cotton wiped clean, ensures ml headspace bottle inwall sample supernatant coating film forming, is used for head space detects with the good sample bottle of rear enclosed.
More preferably, when carrying out dilution process to coating sample, described thinning agent is one or both in butyl acetate, cyclohexanone; Described hardening agent is the hardening agent that this area is commonly used, as the prepolymer of toluene diisocyanate TDI, hexa-methylene isocyanates HDI or methyl diphenylene diisocyanate MDI.Described host is film forming matter and a small amount of diluting solvent, coloured, is mixed with metal or organic toner.
The preparation method of above-mentioned treated coating sample is: get the thinning agent of certain volume in the graduated color comparison tube of band, hardening agent and/or diluting solvent and coating is taken successively according to construction ratio, eddy mixer mixes, only get supernatant after putting a period of time to be analyzed, described diluting solvent is Tianna solution or banana oil.
The preparation how carrying out sample with adopt which kind of effective sample injection method by the consistent key factor admitted as being gas chromatography successful analysis, the present invention is in order to reach the object of the halogenated hydrocarbons in accurate and sensitive detection coating, improvement sampling mode has been carried out to coating sample to be measured, first be how to obtain reappearing and the representative coating sample detected for headspace gas, for coating sample in prior art, often can adopt suitable thinning agent to its dilution to facilitate detection, its conventional thinning agent has silicone oil, acetonitrile, ethyl acetate etc., but for different types of coating, need to select different thinning agents, whether thinning agent fully can have considerable influence to analysis testing result by solubilized target coating, the present invention is directed to different coating, coating is mixed from different thinning agent, to obtain preferably disperse dilution effect for analyzing detection coating sample.
Secondly the sample injection method for coating sample also needs to do a lot of consideration, because of the character of coating itself, it is made to be different from general fixing or liquid substance, when carrying out headspace sampling, need significant care, in prior art, a certain amount of just beginning after ml headspace bottle is also got as conventional sample for coating sample and detect analysis, this operation not only makes vaporized content in thing to be detected tail off, also can increase detection time and testing cost, cause testing result deviation larger, and the present invention optimizes the flow process of sampling on the basis of existing technology, make sampling operation more rationally easy, institute's sample thief also has better representativeness, consider ductility and the coating of coating sample simultaneously, be coated with after coating sample being added ml headspace bottle, make coating sample dispersed in ml headspace bottle, this painting work is conducive to the release of volatile organic matter in ml headspace bottle in sample, makes testing result more accurate.
The method of the low boiling halogenated hydrocarbons in HS GC mass spectrometric determination solvent wood coatings is provided, comprises the following steps:
S1. sample pretreating: the thinning agent getting certain volume, in color comparison tube, takes each component of coating to be measured successively according to construction ratio and mixes;
S2. headspace sampling: left standstill by the potpourri that S1 obtains, get supernatant in ml headspace bottle, is assisted by the gravity flow of sample supernatant or instrument, makes sample supernatant be evenly distributed on ml headspace bottle inwall, removes redundant sample supernatant and closes ml headspace bottle;
S3. sample determination: adopt HS GC mass spectroscopy, wherein:
Head space condition is: head space equilibrium temperature 80 ~ 120 DEG C, balance 10 ~ 20min, sampling probe 100 ~ 125 DEG C, and transmission line temperature is 120 ~ 135 DEG C;
GC conditions is: chromatographic column is 5% phenyl/95% methylsiloxane capillary column, 30m × 0.25mm × 0.25 μm, and post case adopts temperature programme; Initial temperature 30 DEG C keep 12min, then with 10 DEG C/min be warming up to 150 DEG C keep 2min, 30 DEG 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; Quantitative loop volume 1ml; Flow rate of carrier gas: 10 ~ 20ml/min;
Mass Spectrometry Conditions is: ionization mode is electron impact ionization source, and bombardment ability is 70eV; Ion source temperature 230 DEG C; Level Four bar temperature 150 DEG C; GC-MS interface temperature 250 DEG C; Detecting pattern is Salbutamol Selected Ion Monitoring.
Preferably, step S1 gets the suitable thinning agent of certain volume in the graduated color comparison tube of band, takes each component of coating to be measured successively, again weigh, eddy mixer mixes after being settled to scale according to construction ratio; The time that this operation can make each component of coating expose in atmosphere shortens as far as possible, guarantees the representativeness of institute's sample thief, also reduces the speed that the component that can be mutually polymerized carries out reacting.
During above-mentioned detection, sample headspace bottle is after heating, and volatilize diluting solvent and halogenated hydrocarbons, the testing sample after gasification enters in gas chromatograph with inert carrier gas, measures after chromatographic column is separated with mass spectrometer, quantitative with Selective ion mode.3 qualitative ions selected by often kind of halogenated hydrocarbons, wherein comprise a quota ion.
Preferably, S1 is specially the thinning agent of getting certain volume amount in the graduated color comparison tube of band, takes each components such as coating to be measured successively, again weigh, eddy mixer mixes after being settled to scale according to construction ratio.
Preferably, S2 is specially and gets a certain amount of S1 potpourri supernatant and be placed in the 20ml specification ml headspace bottle of known quality, is assisted, make sample supernatant be evenly distributed on ml headspace bottle inwall by the gravity flow of sample supernatant or spreading implement.After being coated with, sample supernatant unnecessary at the bottom of ml headspace bottle is discharged by bottleneck, again weighs after bottleneck absorbent cotton wiped clean, with the good sample bottle of rear enclosed.
The present invention uses the methylene chloride, 1 of concentration known, 1-ethylene dichloride, methenyl choloride, 1,1,1-trichloroethanes, 1,2-ethylene dichloride, phenixin, triclene, 1,1,2-trichloroethanes standard mixed solution, according to above-mentioned sample headspace injection procedure, be introduced into gas chromatograph-mass spectrometer (GCMS), the retention time of record test compound, determine whether there is this compound, then drawing standard curve negotiating Selective ion mode carries out quantitatively by the standard retention time and characteristic ion abundance ratio contrasting test compound.
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, detected parameters in its detection method, as selected thinning agent, head space equilibrium temperature, equilibration time etc. influence each other, finally determine testing result significant difference, concrete for polyurethane coating, its detected parameters can reference example 1, for nitro paint, its detected parameters can reference example 2, and to alkyd paint, its detected parameters can reference example 3.
Compared with prior art, beneficial effect of the present invention:
The present invention provide firstly a kind of method for making sample of coating sample, namely each component of coating to be measured is taken successively in the scale color comparison tube adding thinning agent according to construction ratio, when avoiding the mixing sample operation that GB states, the volatilize homogeneity that causes and the repetition sample preparation of inevitable adjoint solvent cannot ensure conforming defect; Select butyl acetate and cyclohexanone to be thinning agent, the chromatographic peak of butyl acetate, cyclohexanone is separated well with each target peak, thus the interference of the solvent peak avoiding appearance time wider; Testing sample was carried out coating process at ml headspace bottle inwall by the present invention before carrying out HS GC, this method of operating effectively improves sample volatilization condition in ml headspace bottle, ensure that in ml headspace bottle, sample completes gasification within a short period of time, improves the deficiency that common vapor liquid equilibrium Head space needs the long period stable; Adopt headspace sampling, moisture content, high boiling product or nonvolatile confrontation analytical column can be avoided to cause overload and pollution problem, be also conducive to the maintenance and the use cost that reduce gas chromatograph-mass spectrometer (GCMS).Halogenated hydrocarbons and other components well effectively can be separated identification by the present invention, thus can measure halogenated hydrocarbons content separately.The Monitoring lower-cut of single halogenated hydrocarbons is 0.005%, the measured object recovery 90% ~ 105%, linear dependence 0.9993 ~ 0.9997, and the relative deviation of same operator twice measurement result is less than 5%, and between different experiments room, the relative mistake of test result is less than 10%.In this invention, halogenated hydrocarbons detection collection of illustrative plates false positive can clearly judge simultaneously, and sample detection is reproducible, and Selective ion mode is quantitatively accurate, and HS GC mass spectrometer highly versatile, therefore this invention has applicability and realistic meaning widely.
Accompanying drawing explanation
Fig. 1 is the total ion current figure of methylene chloride, 1,1-ethylene dichloride, methenyl choloride, 1,1,1-trichloroethanes, 1,2-ethylene dichloride, phenixin, triclene, 1,1,2-trichloroethanes standard mixed solution; Chromatographic peak order is from left to right followed successively by methylene chloride, 1,1-ethylene dichloride, methenyl choloride, 1,1,1-trichloroethanes, 1,2-ethylene dichloride, phenixin, triclene, 1,1,2-trichloroethanes;
Fig. 2 records 1,1-dichloroethane content and head space equilibration time trend map for different disposal sample described in embodiment 1, and wherein horizontal ordinate is equilibration time, unit min; Ordinate is test result content, unit %;
Fig. 3 records methylene chloride content and head space equilibration time trend map for different disposal sample described in embodiment 2; Wherein, horizontal ordinate is equilibration time, unit min; Ordinate is test result content, unit %.
Embodiment
Below by Figure of description and specific embodiment, the present invention is specifically described further.Simple the substituting of design philosophy of the present invention or allied substances belongs to protection scope of the present invention.If following used experimental technique is without specified otherwise, be the method for the existing routine of the art, the batching used or material, if no special instructions, be by the available batching of commercial sources or material.
the mensuration of halogenated hydrocarbons in embodiment 1 polyurethane coating
Sample construction ratio is host (main paint): hardening agent (TDI): diluting solvent (Tianna solution)=1:0.5:0.5(mass ratio).Get 25ml color-comparison tube, add about 5g(and be accurate to 0.1mg, lower same) butyl acetate, take each component of main paint, TDI and Tianna solution successively according to construction ratio, amount to 5g sample.Potpourri mixes with eddy mixer and leaves standstill, getting supernatant with suction pipe is transferred in clean 20ml specification ml headspace bottle, make sample supernatant gravity flow be applied to ml headspace bottle inwall by rotating ml headspace bottle, redundant sample supernatant is discharged by bottleneck, immediately sealing top empty bottle.Of poor qualityly be defined as 1# sample for secondary sample quality 0.2g(before and after ml headspace bottle coating), directly get above-mentioned mixing sample 0.1g(2# sample), 0.5g(3# sample), 1.0g(4# sample) be placed at the bottom of ml headspace bottle, according to GB 18581-2009 Appendix B test specimens (5# sample).Above-mentioned test specimens equal parallel testing twice, calculating mean value and deviation.
The ml headspace bottle made is used for HS GC mass spectrum, and HS GC mass spectrometer condition of work is as follows:
A () head space equilibrium temperature 80 DEG C, balances 10min, 20min, 30min, 40min, 50min, 60min successively, sampling probe 100 DEG C, and transmission line temperature is 120 DEG C, and carrier gas is high-purity helium; Quantitative loop volume 1ml; Flow rate of carrier gas 20ml/min.
(b) gas chromatographic sample introduction mouth temperature 120 DEG C; Sample injection time 1.5min; Split ratio 1:1.
(c) chromatographic column: the capillary chromatographic column of 30m × 0.25mm × 0.25 μm, 5% phenyl/95% methylsiloxane capillary column; Carrier gas flux 1.00ml/min(constant rate).
(d) column temperature: initial temperature 30 DEG C keep 12min, then with 10 DEG C/min be warming up to 150 DEG C keep 2min, 30 DEG C/min be warming up to 180 DEG C keep 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 monitor: 3 qualitative ions selected by often kind of halogenated hydrocarbons, wherein comprise a quota ion, halogenated hydrocarbons monitoring ion includes but not limited to compound described in table 1 see the object-low boiling halogenated hydrocarbons of table 1(detection of the present invention).
By with halogenated hydrocarbons standard appearance time and characteristic ion abundance ratio, determine in sample containing 1,1-ethylene dichloride, triclene, adopt external standard method according to target ion peak areas calculating, record 1,1-dichloroethane content and head space equilibration time trend are as Fig. 2, and the painting work of result display 1# sample has a clear superiority in for shortening head space equilibration time, raising analytical test efficiency.Table 2 all reaches the replicate test result table of comparisons after equilibration time for each test specimens, as can be seen from table 2 also, is coated with test specimens and has good reappearance, and have less standard deviation in the ml headspace bottle of 1#.
the mensuration of halogenated hydrocarbons in embodiment 2 nitro paint
Sample construction ratio is host: diluting solvent=1:0.2(mass ratio).Get 25ml color-comparison tube, add 5.0g cyclohexanone, take alkyd resin (host) and Tianna solution (diluting solvent) successively according to construction ratio, amount to 5.0g sample.Potpourri mixes with eddy mixer and leaves standstill, with suction pipe, sample supernatant is transferred in clean 20ml specification ml headspace bottle, make sample supernatant gravity flow be applied to ml headspace bottle inwall by rotating ml headspace bottle, redundant sample supernatant is discharged by bottleneck, subsequently sealing top empty bottle.Of poor quality for secondary sample quality 0.2g(1# sample before and after ml headspace bottle coating), directly get above-mentioned mixing sample 0.1g(2# sample), 0.5g(3# sample), 1.0g(4# sample) be placed at the bottom of ml headspace bottle, according to GB 18581-2009 Appendix B test specimens (5# sample).Above-mentioned test specimens equal parallel testing twice, calculating mean value and deviation.
The ml headspace bottle made is used for HS GC mass spectrum, and HS GC mass spectrometer condition of work is as follows:
A () head space equilibrium temperature 100 DEG C, balances 10min, 20min, 30min, 40min, 50min, 60min successively, sampling probe 110 DEG C, and transmission line temperature is 120 DEG C, and carrier gas is high-purity helium; Quantitative loop volume 1ml; Flow rate of carrier gas 20ml/min.
(b) gas chromatographic sample introduction mouth temperature 120 DEG C; Sample injection time 1.5min; Split ratio 2:1.
(c) chromatographic column: the capillary chromatographic column of 30m × 0.25mm × 0.25 μm, 5% phenyl/95% methylsiloxane capillary column; Carrier gas flux: 1.00ml/min(constant rate).
(d) column temperature: initial temperature 30 DEG C keep 12min, then with 10 DEG C/min be warming up to 150 DEG C keep 2min, 30 DEG C/min be warming up to 180 DEG C keep 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 monitor: 3 qualitative ions selected by often kind of halogenated hydrocarbons, wherein comprise a quota ion, halogenated hydrocarbons monitoring ion includes but not limited to compound described in table 1 see the object-low boiling halogenated hydrocarbons of table 1(detection of the present invention).
By with halogenated hydrocarbons standard appearance time and characteristic ion abundance ratio, determine in sample containing methylene chloride, 1,1,2-trichloroethanes, adopt external standard method according to target ion peak areas calculating, record methylene chloride content and head space equilibration time trend as Fig. 3, the painting work of result display 1# sample for shortening head space equilibration time, improve analytical test efficiency and have a clear superiority in.
Table 3 all reaches the replicate test result after equilibration time for each test specimens and according to the GB 18581-2009 Appendix B method test result table of comparisons, equally, in the ml headspace bottle of 1#, coating test specimens has good reappearance, and has less standard deviation.
the mensuration of halogenated hydrocarbons in embodiment 3 alkyd paint
Sample construction ratio is host: diluting solvent=1:0.5.Get 25ml color-comparison tube, add the butyl acetate cyclohexanone mixed solvent of 5.0g volume ratio 1:1, take alkyd resin (host) and banana oil (diluting solvent) successively according to construction ratio, amount to 5g sample.Potpourri mixes with eddy mixer and leaves standstill, with suction pipe, sample supernatant is transferred in clean 20ml specification ml headspace bottle, make sample supernatant gravity flow be applied to ml headspace bottle inwall by rotating ml headspace bottle, redundant sample supernatant is discharged by bottleneck, subsequently sealing top empty bottle.The of poor quality of ml headspace bottle coating front and back is secondary sample quality 0.2g, and parallel experiment six times, calculating mean value and RSD, be defined as S test specimens.Simultaneously carry out contrast test according to GB 18581-2009 Appendix B method of testing: A sample, to test according to after construction ratio mixing sample general assembly (TW) 5g; B sample, to test according to after construction ratio mixing sample general assembly (TW) 10g; C sample, to test according to after construction ratio mixing sample general assembly (TW) 20g; D sample, to test according to after construction ratio mixing sample general assembly (TW) 30g; E sample, to test according to after construction ratio mixing sample general assembly (TW) 40g;
The ml headspace bottle made is used for HS GC mass spectrum, and HS GC mass spectrometer condition of work is as follows:
(a) head space equilibrium temperature 120 DEG C, balance 15min, sampling probe 125 DEG C, transmission line temperature is 135 DEG C, and carrier gas is high-purity helium; Quantitative loop volume 1ml; Flow rate of carrier gas 15ml/min.
(b) gas chromatographic sample introduction mouth temperature 150 DEG C; Sample injection time 1.5min, split ratio 1:1.
(c) chromatographic column: the capillary chromatographic column of 30m × 0.25mm × 0.25 μm, 5% phenyl/95% methylsiloxane capillary column; Carrier gas flux: 1.00ml/min(constant rate).
(d) column temperature: initial temperature 30 DEG C keep 12min, then with 10 DEG C/min be warming up to 150 DEG C keep 2min, 30 DEG C/min be warming up to 180 DEG C keep 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 monitor: 3 qualitative ions selected by often kind of halogenated hydrocarbons, wherein comprise a quota ion, halogenated hydrocarbons monitoring ion includes but not limited to compound described in table 1 see the object-low boiling halogenated hydrocarbons of table 1(detection of the present invention).
By with halogenated hydrocarbons standard appearance time and characteristic ion abundance ratio, determine in sample containing the methenyl choloride of 0.057% and 1,1, the 1-trichloroethanes of 0.025%, adopt external standard method according to target ion peak areas calculating, result, mean value and RSD value that methenyl choloride is tested are as table 4.
Result shows, and the test value adding the S test specimens of each component in target diluting solvent according to construction ratio is successively higher, and has less RSD value, and replicate determination favorable reproducibility is described; And according in GB18581-2009 Appendix B method testing, the sample of a small amount of mixing has larger uncertainty when repeated test, the obvious effect that thinning agent volatilization etc. brings, only strengthening the sample size of mixing and in very short time, completing mixing and sample operation and could reduce this uncertainty to a certain extent, this can cause the reduction of workload increasing and the efficiency of testing, and increases testing cost and burden.
Claims (5)
1. a headspace sampling method for solvent wood coatings, is characterized in that, is left standstill by treated coating sample, get supernatant in ml headspace bottle, assisted by the gravity flow of supernatant or instrument, make it be evenly distributed on ml headspace bottle inwall, remove unnecessary supernatant, close ml headspace bottle and be used for head space detection.
2. headspace sampling method according to claim 1, it is characterized in that, get a certain amount of treated coating sample to leave standstill, get supernatant in ml headspace bottle, assisted by the gravity flow of sample supernatant or spreading implement, sample supernatant is made to be evenly distributed on ml headspace bottle inwall, after being coated with, sample supernatant unnecessary at the bottom of ml headspace bottle is discharged by bottleneck, again weigh after bottleneck absorbent cotton wiped clean, ensure ml headspace bottle inwall sample supernatant coating film forming, be used for head space with the good sample bottle of rear enclosed and detect.
3. headspace sampling method according to claim 1, is characterized in that, the disposal route of described coating sample is, the thinning agent getting certain volume, in color comparison tube, takes each component of coating to be measured successively according to construction ratio and mixes.
4. headspace sampling method according to claim 3, is characterized in that, described thinning agent is one or both in butyl acetate, cyclohexanone.
5. the method for the low boiling halogenated hydrocarbons in HS GC mass spectrometric determination solvent wood coatings, is characterized in that, comprise the following steps:
S1. sample pretreating: the thinning agent getting certain volume, in color comparison tube, takes each component of coating to be measured successively according to construction ratio and mixes;
S2. headspace sampling: left standstill by the potpourri that S1 obtains, get supernatant in ml headspace bottle, is assisted by the gravity flow of sample supernatant or instrument, makes sample supernatant be evenly distributed on ml headspace bottle inwall, removes redundant sample supernatant and closes ml headspace bottle;
S3. HS GC mass spectroscopy is adopted to detect being arranged in closed ml headspace bottle sample supernatant.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106990190A (en) * | 2016-11-15 | 2017-07-28 | 惠州市长润发涂料有限公司 | A kind of method for determining volatile organic content in coating paint film |
| 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 |
| 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 |
| CN111007182A (en) * | 2019-12-30 | 2020-04-14 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101688002A (en) * | 2007-02-20 | 2010-03-31 | 塞尔瑞星技术有限公司 | Combination of substituted cyclodextrin compound and activated carbon |
| US20110098376A1 (en) * | 2008-06-13 | 2011-04-28 | Sheerin Robert J | Aqueous Coating Compositions with De Minimis Volatile Emissions |
| CN102101975A (en) * | 2009-12-16 | 2011-06-22 | 罗门哈斯公司 | Low odor compositions and low odor coating compositions |
| CN102478558A (en) * | 2010-11-25 | 2012-05-30 | 中国检验检疫科学研究院 | Method for determining five volatile organic compounds in paint |
-
2014
- 2014-10-11 CN CN201410534867.5A patent/CN104359997B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101688002A (en) * | 2007-02-20 | 2010-03-31 | 塞尔瑞星技术有限公司 | Combination of substituted cyclodextrin compound and activated carbon |
| US20110098376A1 (en) * | 2008-06-13 | 2011-04-28 | Sheerin Robert J | Aqueous Coating Compositions with De Minimis Volatile Emissions |
| CN102101975A (en) * | 2009-12-16 | 2011-06-22 | 罗门哈斯公司 | Low odor compositions and low odor coating compositions |
| CN102478558A (en) * | 2010-11-25 | 2012-05-30 | 中国检验检疫科学研究院 | Method for determining five volatile organic compounds in paint |
Non-Patent Citations (4)
| Title |
|---|
| 中华人民共和国国家质量监督检验总局 等: "《中华人民共和国国家标准 GB/T23992-2009》", 2 June 2009 * |
| 中国建筑材料检验认证中心 等: "《装饰装修材料中有害物质检测技术》", 30 November 2008, 中国计量出版社 * |
| 吕庆 等: "顶空气相色谱-质谱法测定涂料中的5种挥发性有机物", 《分析测试学报》 * |
| 张伟亚 等: "顶空进样气质联用法测定涂料中12种卤代烃和苯系物", 《分析化学》 * |
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|---|---|---|---|---|
| CN106990190A (en) * | 2016-11-15 | 2017-07-28 | 惠州市长润发涂料有限公司 | A kind of method for determining volatile organic content in coating paint film |
| 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 |
| 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 |
| CN111007182A (en) * | 2019-12-30 | 2020-04-14 | 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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