CN103926352B - Extraction standard correction-gas chromatography-mass spectrography the assay method of 12 kinds of phthalic esters in a kind of hot melt adhesive - Google Patents
Extraction standard correction-gas chromatography-mass spectrography the assay method of 12 kinds of phthalic esters in a kind of hot melt adhesive Download PDFInfo
- Publication number
- CN103926352B CN103926352B CN201410189321.0A CN201410189321A CN103926352B CN 103926352 B CN103926352 B CN 103926352B CN 201410189321 A CN201410189321 A CN 201410189321A CN 103926352 B CN103926352 B CN 103926352B
- Authority
- CN
- China
- Prior art keywords
- kinds
- hot melt
- melt adhesive
- phthalic
- extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
Extraction standard correction-gas chromatography-mass spectrography the assay method of 12 kinds of phthalic esters in a kind of hot melt adhesive, it is characterized in that: with scissors, hot melt adhesive sample is shredded, be placed in normal hexane, after ultrasonic extraction, get supernatant after centrifugal-dispersive solid-phase extraction purification, by extraction standard correction-gas chromatograph-mass spectrometer (GCMS) (GC/MS), inner mark method ration is adopted to detect the content of 12 kinds of phthalic esters in hot melt adhesive.This method has easy and simple to handle, fast, and highly sensitive and reproducible advantage, detect and be limited to 0.3-16.0 mg/kg, quantitatively be limited to 0.8-48.0 mg/kg, average recovery of standard addition is 92.13%-103.13%, and mean relative deviation (RSD) is 3.84%-13.74%.
Description
Technical field
The present invention relates to hot melt adhesive chemical constituents determination method, be specifically related to the extraction standard correction-gas chromatography-mass spectrography assay method of 12 kinds of phthalic esters in a kind of hot melt adhesive.
Background technology
Phthalic ester (PAEs), with its excellent performance and cheap price, is widely used in toy, packaging material for food, vinyl flooring, wallpaper, detersive, in the chemical products such as lubricating oil and personal-care supplies (Anal Bioanal Chem, 2003,375:527 ~ 533.).PAEs is a class endocrine disruption hormone, cell mutation can be caused, canceration and teratogenesis, be proved in toxicologic study in vitro to have and intend weak estrogen action, can cause damage to male reproductive system, cause a series of male reproduction toxicity performance such as Serum testosterone concentrations decline, the minimizing of Sperm specific enzyme quantity, genital malformation, and increase the incidence of disease (the Environ. Health. Perspect. of women with breast cancer, 2003,111 (2): 139 ~ 145).PAEs adsorbability and compatibility stronger, and be generally be present in polymkeric substance in the mode of physisorption instead of chemical bonding usually used as the phthalic ester of plasticiser, therefore, under certain condition, easily move out and entered environment (Environ. Sci. Technol. from carrier, 2013,47 (21): 12459 ~ 12468.).Within 2011, Taiwan plasticiser disturbance gets more and more people's extensive concerning by the Product quality and safety that PAEs is relevant.At present, many countries start to pay close attention to PAEs and to food, move from food contact material the harm brought, and the specific transfer of part PAEs in food contact material is limited the quantity (Specific Migration Limit, SML) be limited (GB 9685-2008, food containers, wrappage adjuvant use hygienic standard).
Hot melt adhesive is widely used in the bookbinding of wooden, paper material and the field such as car and boat, building interior trim, and exist and human body, the possibility of the contact such as food, but, current China there is no the hygienic standard of PAEs in hot melt adhesive, also correlative study and detection method is lacked, so, be necessary the assay method of the phthalate compound set up in a kind of hot melt adhesive.
Summary of the invention
Object of the present invention is intended to the defect overcoming prior art, the extraction standard correction-gas chromatography-mass spectrography assay method of 12 kinds of phthalic esters in a kind of hot melt adhesive of specialized designs.This detection method effectively eliminates the matrix effect that hot melt adhesive kind phthalic ester detects, and has easy and simple to handle, fast, highly sensitive, repeatability and the good advantage of the recovery.
The object of the invention is to realize by the following technical programs:
Extraction standard correction-gas chromatography-mass spectrography the assay method of 12 kinds of phthalic esters in a kind of hot melt adhesive, that hot melt adhesive sample is shredded, be placed in normal hexane, leave standstill after ultrasonic extraction, by gas chromatograph-mass spectrometer (GCMS) (GC/MS), adopt extraction standard correction-inner mark method ration to detect the content of 12 kinds of phthalic esters in hot melt adhesive, concrete steps are as follows:
1) extraction of phthalic ester in hot melt adhesive sample: hot melt adhesive sample is shredded, is placed in normal hexane, ultrasonic extraction;
2) purification of extract: get supernatant, purifies through dispersive solid-phase extraction (d-SPE) after centrifugal;
3) matrix calibration standard working solution preparation: get 12 kinds of phthalic ester standard items, with n-hexane dissolution constant volume, after stepwise dilution, add interior mark liquid and bare substrate, is mixed with the standard working solution of the 12 kinds of phthalic esters adding bare substrate;
4) gas chromatography-mass spectrometry analysis: utilize gas chromatograph-mass spectrometer (GCMS) to carry out detection to matrix calibration standard working solution and extract and analyze;
5) Specification Curve of Increasing and result calculate.
12 kinds of described phthalic esters are specially: phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethoxy) ethyl ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), butyl benzyl phthalate (BBP), phthalic acid two (2-butoxy) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2-ethyl) own ester (DEHP), diphenyl phthalate (BP), di-n-octyl phthalate (DNOP), dinonyl phthalate (DNP), diisononyl phthalate (DINP).
Be designated as Ergol in described, the concentration be inside marked in matrix calibration standard working solution and extract is 1-10 μ g/mL.
The purification of extract comprises the steps: that extract is centrifugal after leaving standstill, get supernatant and be placed in dispersive solid-phase extraction (d-SPE) centrifuge tube containing N-propyl group ethylenediamine (PSA) and florisil silica (Florisil), on whirlpool mixed instrument after vortex oscillation, then high speed centrifugation 2-10 min.
Gas chromatography-mass spectrum condition is: chromatographic column: capillary chromatographic column, Stationary liquid: 5% phenyl/95% methyl polysiloxane, specification: 30 mm × 0.25 μm, m × 0.25; Injector temperature: 280 DEG C; Sample size: 1 μ L, split sampling (split ratio: 10:1); Carrier gas: helium (purity >=99.999%), constant current mode, flow velocity: 1.0 mL/min; Heating schedule: initial temperature 60 DEG C, keeps 1 min, with the speed to 220 DEG C of 20 DEG C/min, keeps 1 min, then with the speed to 280 DEG C of 5 DEG C/min, keeps 15 min; Ionization mode: electron bombardment ionization source (EI); Ionizing energy: 70 eV; Transmission line temperature: 280 DEG C; Ion source temperature: 230 DEG C; Quadrupole rod temperature: 150 DEG C; Mensuration mode: Selective ion mode surveillance style (SIM) scans; Solvent delay: 6 min.12 kinds of phthalic esters and the quantitative and qualitative Selective ion mode of internal standard compound are shown in
table 1:
table 1:12 kinds of phthalic esters and the quantitative and qualitative Selective ion mode table of internal standard compound
The collocation method of matrix calibration standard working solution is: 12 kinds of phthalic ester mixed standard solutions are after stepwise dilution, add mark liquid and bare substrate in Ergol, be mixed with the standard working solution with gradient concentration of 12 kinds of phthalic esters, be specially: 0.04 μ g/mL, 0.1 μ g/mL, 0.2 μ g/mL, 0.5 μ g/mL, 1 μ g/mL, 2 μ g/mL, 4 μ g/mL.
The detection limit of the inventive method and quantitative limit:
The matrix calibration standard working solution of preparation 12 kinds of phthalic esters, regretional analysis is carried out with internal standard compound and its respective concentration of chromatographic peak area comparison after GC/MS analyzes, draw typical curve and regression equation, related coefficient, calibration curve, shown in table 2, and be detection limit when utilizing signal to noise ratio (S/N ratio) to be 3, be quantitative limit when signal to noise ratio (S/N ratio) is 10.By
table 2known, the chromatographic condition adopted makes 12 kinds of phthalate compounds and interior mark all be separated well, and all has good correlativity (R
2> 0.995), detect and be limited to 0.3-16.0 mg/kg, be quantitatively limited to 0.8-48.0 mg/kg.
table 2: the typical curve of 12 kinds of phthalic esters, detection limit and quantitative limit
The repeatability of the inventive method and recovery of standard addition:
Adopt this method to carry out recovery of standard addition experiment, 3 parts, heat-obtaining melten gel sample, add 12 kinds of phthalic ester standard items according to basic, normal, high three kinds of levels respectively, each Pitch-based sphere replication 5 samples.Sample after mark-on carries out pre-treatment respectively and GC/MS analyzes, and by adding scalar and the mark-on measured quantity calculating recovery, the results are shown in Table 3.As known from Table 3, the average recovery of standard addition of 12 kinds of phthalic esters is between 92.13%-103.13%, and average relative standard's deviation (RSD), between 2.10%-8.58%, shows that this method accuracy is high, reproducible, is applicable to quantitatively.
table 3: the recovery of standard addition of 12 kinds of phthalic esters and relative standard deviation
| Sequence number | Compound | Average recovery of standard addition (%) | Average relative standard's deviation (RSD, %) |
| 1 | BMPP | 96.61 | 8.60 |
| 2 | DEEP | 98.52 | 9.68 |
| 3 | DPP | 96.30 | 3.84 |
| 4 | DHXP | 95.25 | 5.45 |
| 5 | BBP | 95.28 | 9.06 |
| 6 | DBEP | 92.17 | 5.97 |
| 7 | DCHP | 95.53 | 9.74 |
| 8 | DEHP | 92.13 | 11.70 |
| 9 | BP | 96.06 | 13.74 |
| 10 | DNOP | 97.19 | 7.83 |
| 11 | DNP | 94.84 | 3.68 |
| 12 | DINP | 103.13 | 8.36 |
Instant invention overcomes the defect of prior art, there is following excellent results:
1. the invention provides a kind of extraction standard correction-gas chromatography-mass spectrography method measuring 12 kinds of phthalate compounds in hot melt adhesive, easy and simple to handle, fast, highly sensitive, repeatability and the recovery good.
2. the present invention compares mechanical shaking extraction, ultrasonic extraction and surname extraction three kinds of extracting modes, found that, take normal hexane as Extraction solvent, under mechanical shaking extraction and soxhlet extraction, hot melt adhesive cannot fully be pulverized or dissolve in 5 h, and after ultrasonic extraction 60 min, hot melt adhesive can fully be pulverized or dissolve.Therefore select ultrasonicly to be extracted as extraction means.
3. use normal hexane for extract in inventive samples pretreatment process, compare methyl alcohol, methylene chloride, methenyl choloride, ethyl acetate, the common solvent such as acetonitrile, hot melt adhesive sample fully can be broken into and cotton-shapedly even dissolve, extraction efficiency is high, and decreases dissolving and the interference of impurity as far as possible.
4. in inventive samples pretreatment process, dispersive solid-phase extraction (d-SPE) mode of extract through the 25 mg florisil silicas (Florisil) containing 25 mg N-propyl group ethylenediamine (PSA) is purified, effectively simple, time saving and energy saving, compare Solid-Phase Extraction (SPE), significantly decrease the use of solvent, reduce the interference of phthalic ester in environment as far as possible.
5. the present invention adopts extraction standard bearing calibration to reduce matrix effect, and method is simply effective, as shown in Figure 3.
Accompanying drawing explanation
Fig. 1 is operational flowchart of the present invention.
Fig. 2 is 12 kinds of phthalic ester standard solution chromatograms, in Fig. 2: 1:BMPP; 2:DEEP; 3:DPP; 4:DHXP; 5:BBP; 6:DBEP; 7:DCHP; 8:DEHP; 9:BP; 10:DNOP; 11:DNP; 12:DINP.
Fig. 3 is recovery comparison diagram before and after matrix corrects.
Embodiment
The present invention is further described by following specific embodiment, but does not limit the present invention.
1. instrument, reagent and instrument condition of work
1) instrument
Gas chromatograph-mass spectrometer (GCMS) (U.S. Agilent 7890A-5975C type); AE163 electronic balance (sensibility reciprocal: 0.0001 g, Mettler company of Switzerland); Ultrasonic generator (KQ-700DB type numerical control ultrasonic cleaner); Germany SIGMA 3-30K-high speed desktop frozen type hydro-extractor.
2) reagent
Normal hexane, chromatographically pure, 12 kinds of phthalic ester standard items: phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethoxy) ethyl ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), butyl benzyl phthalate (BBP), phthalic acid two (2-butoxy) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2-ethyl) own ester (DEHP), diphenyl phthalate (BP), di-n-octyl phthalate (DNOP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), Ergol, N-propyl group ethylenediamine adsorbent (PSA, Agilent), florisil silica adsorbent (Florisil, Agilent).
3) gas chromatography-mass spectrum condition: chromatographic column: capillary chromatographic column, Stationary liquid: 5% phenyl/95% methyl polysiloxane, specification: 30 mm × 0.25 μm, m × 0.25; Injector temperature: 280 DEG C; Sample size: 1 μ L, split sampling (split ratio: 10:1); Carrier gas: helium (purity >=99.999%), constant current mode, flow velocity: 1.0 mL/min; Heating schedule: initial temperature 60 DEG C, keeps 1 min, with the speed to 220 DEG C of 20 DEG C/min, keeps 1 min, then with the speed to 280 DEG C of 5 DEG C/min, keeps 15 min; Ionization mode: electron bombardment ionization source (EI); Ionizing energy: 70 eV; Transmission line temperature: 280 DEG C; Ion source temperature: 230 DEG C; Quadrupole rod temperature: 150 DEG C; Mensuration mode: Selective ion mode surveillance style (SIM) scans; Solvent delay: 6 min.
4) bare substrate corrects the preparation of standard working solution and the determination of standard working curve
A) inner mark solution: preparation Benzyl Benzoate ester concentration is about the hexane solution of 1 mg/mL.
B) 12 kinds of phthalic ester mixed standard solutions I: take 0.02 g(respectively and be accurate to 0.1 mg) 12 kinds of phthalic ester standard items, be placed in same 10 mL volumetric flasks, with n-hexane dissolution and constant volume, be mixed with the mixed standard solution I that each phthalic ester concentration is 2 mg/mL.Keep in Dark Place in 0 DEG C ~ 4 DEG C refrigerators, the term of validity 6 months.
C) 12 kinds of phthalic ester mixed standard solutions II: accurately pipette 0.1 mL mixed standard solution I, are placed in 10 mL volumetric flasks, with normal hexane constant volume, are mixed with the mixed standard solution II that each phthalic ester concentration is 20 μ g/mL.Keep in Dark Place in 0 DEG C ~ 4 DEG C refrigerators, the term of validity 6 months.
D) bare substrate preparation: 1 g hot melt adhesive sample is shredded, is placed in 50 mL normal hexanes, extracts 60 min with the frequency ultrasound of 100 Hz, centrifugal after leaving standstill 30 min, get supernatant and be placed in 100 mL conical flasks.
E) preparation of matrix calibration standard working solution: the mixed standard solution II accurately pipetting 0.02 mL, 0.05 mL, 0.1 mL, 0.25 mL, 0.5 mL, 1 mL, 2 mL, be placed in 10 respective mL volumetric flasks, add 5 mL bare substrate more successively, then accurately add 50 μ L inner mark solutions, be settled to scale with normal hexane.Get each gradient matrix calibration standard working solution 1.5 mL, be placed in dispersive solid-phase extraction (d-SPE) centrifuge tube containing 25 mg N-propyl group ethylenediamine (PSA) and 25 mg florisil silicas (Florisil), with rotating speed vortex oscillation 3 min of 2000 rpm on whirlpool mixed instrument, again with centrifugal 5 min of the rotating speed of 10000 rpm, obtain serial matrix calibration standard working solution, its concentration is respectively: 0.04 μ g/mL, 0.1 μ g/mL, 0.2 μ g/mL, 0.5 μ g/mL, 1 μ g/mL, 2 μ g/mL, 4 μ g/mL.
F) determination of standard working curve
GC/MS mensuration is carried out to matrix correction work standard solution, calculate 12 kinds of phthalic esters and interior target peak area ratio in each standard solution, make the typical curve of 12 kinds of phthalic ester concentrations and peak area ratio or calculate regression equation, typical curve should be linear relationship, coefficient R
2should 0.995 be not less than.After often carrying out 20 sample determinations, the Working Standard Solution of an intermediate concentration should be added, if the value measured and initial value differ by more than 5%, then should re-start the making of whole typical curve.
5. the determination of sample pre-treatments and testing result
A) extraction of phthalic ester in hot melt adhesive sample: 0.2 g hot melt adhesive sample is shredded, is placed in 20 mL normal hexanes, extracts 60 min with the frequency ultrasound of 100 Hz;
B) purification of extract: extract is centrifugal after leaving standstill 30 min, get 1.5 mL supernatants and be placed in dispersive solid-phase extraction (d-SPE) centrifuge tube containing 25 mg N-propyl group ethylenediamine (PSA) and 25 mg florisil silicas (Florisil), with rotating speed vortex oscillation 3 min of 2000 rpm on whirlpool mixed instrument, again with centrifugal 5 min of the rotating speed of 10000 rpm, get supernatant and carry out GS/MS analysis.
C) according to instrument test condition working sample, each sample replication twice.
D) in sample the content of 12 kinds of phthalic esters with shown in following formula:
In formula:
x i the content of phthalic ester in-sample, unit is milligrams per kilogram (mg/kg);
c i ---phthalic ester concentration in the sample drawn by typical curve, unit is micrograms per millilitre (μ g/mL);
v---the volume of extract, unit is milliliter (mL);
m---sample mass, unit is gram (g).
Be final measurement result with the mean value of twice replicate determination, be accurate to 0.1 mg/kg.
Its relative average debiation of horizontal survey result should be less than 10%.
Utilize the method provided of the present invention, detect that the content of BMPP in hot melt adhesive A is 3.14 mg/kg, other PAEs does not detect.
Embodiment 2
Assay method according to embodiment 1, detects that in hot melt adhesive B, above-mentioned PAEs does not all detect.
Claims (2)
1. the extraction standard correction-gas chromatography-mass spectrography assay method of 12 kinds of phthalic esters in a hot melt adhesive, it is characterized in that: hot melt adhesive sample is shredded, be placed in normal hexane, leave standstill after ultrasonic extraction, by gas chromatograph-mass spectrometer (GCMS) (GC/MS), adopt extraction standard correction-inner mark method ration to detect the content of 12 kinds of phthalic esters in hot melt adhesive, 12 kinds of phthalic esters are: phthalic acid two (4-methyl-2-amyl group) ester (BMPP), phthalic acid two (2-ethoxy) ethyl ester (DEEP), diamyl phthalate (DPP), dihexylphthalate (DHXP), butyl benzyl phthalate (BBP), phthalic acid two (2-butoxy) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2-ethyl) own ester (DEHP), diphenyl phthalate (BP), di-n-octyl phthalate (DNOP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), concrete steps are as follows:
1) extraction of phthalic ester in hot melt adhesive sample: hot melt adhesive sample is shredded, is placed in normal hexane, ultrasonic extraction;
2) purification of extract: extract is centrifugal after leaving standstill, get supernatant and be placed in dispersive solid-phase extraction (d-SPE) centrifuge tube containing N-propyl group ethylenediamine (PSA) and florisil silica (Florisil), on whirlpool mixed instrument after vortex oscillation, then high speed centrifugation 2-10 min;
3) matrix calibration standard working solution preparation: get 12 kinds of phthalic ester standard items, with n-hexane dissolution constant volume, after stepwise dilution, add interior mark liquid and bare substrate, is mixed with the standard working solution of the 12 kinds of phthalic esters adding bare substrate; Concrete configuration method is: 12 kinds of phthalic ester mixed standard solutions are after stepwise dilution, add mark liquid and bare substrate in Ergol, be mixed with the standard working solution with gradient concentration of 12 kinds of phthalic esters, be specially: 0.04 μ g/mL, 0.1 μ g/mL, 0.2 μ g/mL, 0.5 μ g/mL, 1 μ g/mL, 2 μ g/mL, 4 μ g/mL;
4) gas chromatography-mass spectrometry analysis: utilize gas chromatograph-mass spectrometer (GCMS) to carry out detection to matrix calibration standard working solution and extract and analyze;
Gas chromatography-mass spectrum condition is: chromatographic column: capillary chromatographic column, Stationary liquid: 5% phenyl/95% methyl polysiloxane, specification: 30 mm × 0.25 μm, m × 0.25; Injector temperature: 280 DEG C; Sample size: 1 μ L, split sampling, split ratio: 10:1; Carrier gas: helium, purity >=99.999%, constant current mode, flow velocity: 1.0 mL/min; Heating schedule: initial temperature 60 DEG C, keeps 1 min, with the speed to 220 DEG C of 20 DEG C/min, keeps 1 min, then with the speed to 280 DEG C of 5 DEG C/min, keeps 15 min; Ionization mode: electron bombardment ionization source (EI); Ionizing energy: 70 eV; Transmission line temperature: 280 DEG C; Ion source temperature: 230 DEG C; Quadrupole rod temperature: 150 DEG C; Mensuration mode: Selective ion mode surveillance style (SIM) scans; Solvent delay: 6 min;
5) Specification Curve of Increasing and result calculate.
2. the extraction standard correction-gas chromatography-mass spectrography assay method of 12 kinds of phthalic esters in hot melt adhesive according to claim 1, it is characterized in that, be designated as Ergol in described, the concentration be inside marked in matrix calibration standard working solution and extract is 1-10 μ g/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410189321.0A CN103926352B (en) | 2014-05-06 | 2014-05-06 | Extraction standard correction-gas chromatography-mass spectrography the assay method of 12 kinds of phthalic esters in a kind of hot melt adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410189321.0A CN103926352B (en) | 2014-05-06 | 2014-05-06 | Extraction standard correction-gas chromatography-mass spectrography the assay method of 12 kinds of phthalic esters in a kind of hot melt adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103926352A CN103926352A (en) | 2014-07-16 |
| CN103926352B true CN103926352B (en) | 2015-08-26 |
Family
ID=51144647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410189321.0A Active CN103926352B (en) | 2014-05-06 | 2014-05-06 | Extraction standard correction-gas chromatography-mass spectrography the assay method of 12 kinds of phthalic esters in a kind of hot melt adhesive |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103926352B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105651898A (en) * | 2016-03-29 | 2016-06-08 | 阿特斯(中国)投资有限公司 | Method for testing cross-linking agent content in EVA (ethylene vinyl acetate copolymer) film |
| CN107655991B (en) * | 2017-09-21 | 2020-02-11 | 国家烟草质量监督检验中心 | Method for measuring 6 kinds of phthalate in soil |
| CN108008028B (en) * | 2017-11-13 | 2020-08-14 | 浙江省海洋水产研究所 | Dispersed solid phase extraction-gas chromatography-mass spectrometry detection method for phthalate ester environmental hormone in marine products |
| CN108680691B (en) * | 2018-05-15 | 2020-06-19 | 国家烟草质量监督检验中心 | Method for determining phthalate in tobacco flavor and fragrance |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001098242A (en) * | 1999-09-28 | 2001-04-10 | Sekisui Chem Co Ltd | Reactive hot-melt adhesive composition |
| CN101805569B (en) * | 2009-10-23 | 2012-02-22 | 郑州中原应用技术研究开发有限公司 | Transparent butyl hot-melt sealant and preparation method thereof |
-
2014
- 2014-05-06 CN CN201410189321.0A patent/CN103926352B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103926352A (en) | 2014-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104316634B (en) | The measuring method of volatile organic acids in a kind of cigarette mainstream flue gas | |
| CN103926352B (en) | Extraction standard correction-gas chromatography-mass spectrography the assay method of 12 kinds of phthalic esters in a kind of hot melt adhesive | |
| CN105866267B (en) | The extraction of residual solvent, detection method and kit and purposes in packaging material | |
| CN104991017B (en) | Liquid chromatogram-tandem mass spectrometry method for determining isothiazolinone bactericides contained in water-based adhesive | |
| CN109470791A (en) | A kind of method and kit of high performance liquid chromatography-tandem mass detection serum estradiol | |
| CN103926354B (en) | Gas chromatography-mass spectrometry determination method for six phthalates in hot melt adhesive | |
| TAN et al. | Analysis of 13 kinds of steroid hormones in raw milk using modified QuEChERS method combined with UPLC-QTOF-MS | |
| CN104614466B (en) | The assay method of antiseptic in tobacco juice for electronic smoke | |
| CN104535666B (en) | A kind of method adopting gas chromatograph-mass spectrometer (GCMS) to measure 18 kinds of phthalic ester migration amounts in travelling belt | |
| CN103344725B (en) | Method for simultaneously and quantitatively detecting content of ethyl carbamate and phthalate in distilled white wine | |
| Fiamegos et al. | Ultrasonic-assisted derivatization reaction of amino acids prior to their determination in urine by using single-drop microextraction in conjunction with gas chromatography | |
| CN104359998B (en) | A kind of gas chromatography tandem mass spectrometry detects the method for methyl mesylate | |
| Fontell et al. | Some new methods for separation and analysis of fatty acids and other lipids | |
| CN102866223A (en) | Method for determining benzene and methylbenzene residue in nail polish by utilizing headspace-gas-chromatography mass spectrometry | |
| CN111175412A (en) | Method for detecting 16 phthalate plasticizers in children products | |
| CN105974039A (en) | Method for enriching and detecting phthalic acid ester in plastic product for food packaging | |
| Huang et al. | Coupling frontal elution paper chromatography with desorption corona beam ionization mass spectrometry for rapid analysis of chlorphenamine in herbal medicines and dietary supplements | |
| RU2425380C1 (en) | Method of quantitative analysis of urine dimethyl terephthalate by liquid chromatography | |
| CN107688062A (en) | A kind of method of trace nicotine in measure tobacco juice for electronic smoke | |
| CN104198605B (en) | A kind of assay method of cigarette hot melt adhesive phenol antioxidant content | |
| CN102095815A (en) | Method for determining musk xylene in washing products | |
| CN105738513A (en) | Method for detecting relative content of fatty acid in raw milk | |
| CN108535395A (en) | A method of using 32 kinds of free fatties in UPLC-QTof Rapid Simultaneous Determination health liquors | |
| CN104111291A (en) | Detection method of chlopyrifos pesticide and three metabolites thereof in soil | |
| Xun et al. | Simultaneous determination of seven acrylates in food contact paper products by GC/MS and modified QuEChERS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |