CN109142608A - A kind of measuring method of four classes, 34 kinds of plasticizer - Google Patents
A kind of measuring method of four classes, 34 kinds of plasticizer Download PDFInfo
- Publication number
- CN109142608A CN109142608A CN201811226016.9A CN201811226016A CN109142608A CN 109142608 A CN109142608 A CN 109142608A CN 201811226016 A CN201811226016 A CN 201811226016A CN 109142608 A CN109142608 A CN 109142608A
- Authority
- CN
- China
- Prior art keywords
- plasticizer
- kinds
- standard
- sample
- measuring method
- 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.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The invention discloses a kind of measuring methods of four 34 kinds of plasticizer of class in plastic products.This method uses ultrasonic extraction technology, using ethyl acetate as extractant, extracts phthalate, adipic acid esters, phosphoric acid ester, acetyl tributyl citrate esters four classes, 34 kinds of plasticizer in plastic products, extraction mode is simple；Extract liquor is through Gas Chromatography-Mass Spectrometry.Detection method provided by the invention can measure four class plasticizer simultaneously, cover wide, strong applicability, method high sensitivity, simple and quick, and be successfully applied to the detection of plasticizer in practical plastic products.
Description
Technical field
The present invention relates to measuring method technical fields, more particularly to a kind of measuring method of four 34 kinds of plasticizer of class.
Background technique
Statement in this part merely provides background information related with present disclosure, thereby increases and it is possible to not constitute
The prior art.
Plasticizer is a kind of common plastic processing additives, it can increase the plasticity of plastics, improve processing performance, is assigned
Product flexibility.Plasticizer it is many kinds of, two or more plasticizer can only be used in combination, learn from other's strong points to offset one's weaknesses in most cases, with
It obtains best plasticization effect and reaches comprehensive performance requirement.Most common plasticizer mainly has four major class, i.e. O-phthalic
Acid ester type plasticizer, adipic acid ester plasticizer, phosphate plasticizer and citric acid ester plasticizer.
Phthalate compound, that is, phthalate ester, as a kind of maximum plasticizer of usage amount and cold-resistant agent, in day
The production for often and industrially being made an addition to high molecular weight plastic product extensively, it is main such as polyvinyl chloride (PVC), polypropylene (PP), foam
It is used to improve the processing performance and intensity of plastics.Phthalate substance is a kind of environmental hormone, through zoopery table
Bright, phthalic ester plasticizer has female hormone effect to human and animal, can cause endocrine disorder, reproduction occurs
System lesion seriously affects the health of people.World community also establishes specification for phthalate one after another at present,
It causes further to endanger to reduce phthalate to human body, in terms of European Union, the 1999/815/ of announcement in 1999
EEC instruction is put into the related toy for children of the polyvinyl chloride in three years old children's mouth (PVC) and related supplies, six adjacent benzene
Dioctyl phthalate plasticizer must not exceed 0.1% limitation (six plasticizer are as follows: DEHP, DBP, BBP, DINP, DIDP and DNOP).
Adipic acid ester plasticizer belongs to the plasticizer based on the methylene with straight chain, with high plasticizing efficiency and good
Good cold tolerance, therefore it is widely used in the products such as cold resistance agricultural film, Frozen Food Packaging film, wire and cable clad
In.DEHA is a kind of biological endocrine disruptors, may interfere with the secretion of human hormone, long-term accumulation will lead to abnormal in human body
Shape, canceration and mutagenesis, therefore various countries also start to limit the use of adipic acid ester plasticizer.Former State General Administration for Quality Supervision is in 2005
On October 25, in issues No. 155 bulletin, and enterprise is forbidden, using DEHA, enterprise to be forbidden to sell when producing PVC food fresh keeping membrane
PVC food fresh keeping membrane containing DEHA.
Phosphate plasticizer hydrolytic stability is good, and oil resistivity and electrical insulating property are excellent, and resistance to fungoid is high, does not grow bacterium, can
For improving processability, resistance tocrocking, anti-flammability, mildew resistance and the wearability of product in plastic products.As a kind of excellent
Flame-retardant plasticizer, phosphate plasticizer is be especially suitable for the fire-retardant fire proofing additive with belt of coal mine.Using triaryl phosphate
Ester make flame-retardant plasticizer PVC belt be coal mine flame-retardant conveyer belt core, it is nonflammable, and have resistance to fungi
Energy.
Citric acid ester plasticizer volatility is low, hydrolysis, good light stability, with the product very oil resistant of its plasticising and dynamic
Object rouge, and such plasticizer is substantially non-toxic, is therefore particularly suited for being used as food packaging, the effective igelite of beverage
Plasticizer.The most commonly used is tributyl 2-acetylcitrates (ATBC) and tributyl citrate (TBC).As European Union is to youngster
The strict control of phthalic ester plasticizer content in virgin toy, more and more toys use ATBC instead as plasticising
Agent.
At present about the existing many reports of the measurement of plasticizer, object is mostly phthalate, other adipate esters
The report of class plasticizer, phosphate plasticizer and citric acid ester plasticizer etc. is less.Due to the diversity of common plasticizers,
Quality supervision department does not often know which kind of plasticizer manufacturing enterprise is added in the product in actual operation, this to quality supervision department into
Row risk monitoring and control causes certain difficulty.
Therefore the prior art has much room for improvement and develops.
Summary of the invention
Good, high sensitivity that the technical problem to be solved in the present invention is to provide a kind of selectivity, 34 kinds of simple and rapid four class
The measuring method of plasticizer.
The technical solution of the invention is as follows: a kind of measuring method of four 34 kinds of plasticizer of class, comprising the following steps:
S1 sample pre-treatments: being added Extraction solvent in plastic-like, and ultrasound, extract liquor is transferred in volumetric flask, constant volume, uses
Micropore filtering film filtering, upper machine are to be measured；
The preparation of S2 standard reserving solution and working solution: the standard items of four 34 kinds of plasticizer of class are weighed respectively, carry out single mark
The preparation of quasi- stock solution；Secondly, pipetting single standard stock solution constant volume in volumetric flask respectively, four classes, 34 kinds of plasticizer are obtained
Hybrid standard stock solution；Finally, being configured to the mixing with four 34 kinds of plasticizer of class of concentration gradient with organic solvent diluting
Standard working solution；
The analysis of S3 instrument: it is separated and is identified using GC-MS analysis method, using quantified by external standard method；
S4 result calculates: carrying out regression analysis to its respective concentration with the selection ion peak areas of various plasticizer, obtains
Standard curve, working curve linearly dependent coefficient are greater than 0.99, and abscissa is plasticizer concentration, and ordinate is determining for each plasticizer
Measure ion peak areas；To treated, sample is measured, the selection ion peak areas of the various plasticizer measured, substitutes into standard
Curve acquires the content of various plasticizer in sample.
Wherein the qualitative confirmation of 34 kinds of plasticizer be under the instrument condition of setting, i.e., it is to be measured under GC-MS full scan mode
The selection quasi-molecular ions of liquid and hybrid standard working solution (± 0.2min) at identical retention time occurs, and corresponding ms fragment
The mass-to-charge ratio of ion is consistent with hybrid standard working solution.
The specific operation process of wherein S1, sample pre-treatments are as follows: taking 5g~10g sample, shredded to 0.25cm*
0.25cm is hereinafter, mix；It weighs 1.0g sample to be placed in conical flask, addition 25mL ethyl acetate, the ultrasound 30min at 45 DEG C,
Then extract liquor is transferred in 50mL volumetric flask, residue is washed 3 times with a small amount of ethyl acetate, and combining extraction liquid is settled to
50mL。
The process for preparation of S2 Plays stock solution and working solution is as follows:
34 kinds of each 100.0mg of plasticizer standard items are accurately weighed respectively, are respectively placed in 100mL volumetric flask, with acetic acid second
Ester is diluted to scale, mixes, is configured to the standard reserving solution of 1.0g/L, stored refrigerated at 4 DEG C；Then, various increasings are accurately pipetted
Agent standard reserving solution 10mL is moulded into 100mL volumetric flask, with ethyl acetate constant volume, is configured to the hybrid standard deposit of 100mg/L
It is stored refrigerated at 4 DEG C of liquid；Finally, being diluted to 0.5 μ g/L, 10 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/ step by step with ethyl acetate
L, the hybrid standard working solution of 500 μ g/L series of concentrations.
The GC-MS analysis condition of S3 Instrumental analysis is as follows:
A) chromatographic column: 30m*0.25mm*0.25 μm of DB-5MS capillary column or suitable person；
B) chromatogram column temperature:, keeping 1min by 90 DEG C of initial temperature, rises to 200 DEG C with 15 DEG C/min, retains 2min, then with 15
DEG C/min rises to 235 DEG C, retain 8min, then rise to 250 DEG C with 5 DEG C/min, keeps 2min, finally rise to 300 with 20 DEG C/min
DEG C, keep 7.3min；
C) injector temperature: 250 DEG C；
D) chromatography-mass spectroscopy interface temperature: 250 DEG C；
E) ion source temperature: 250 DEG C；
F) carrier gas: helium, purity >=99.999%；Flow velocity, 1.0mL/min；
G) sample volume: 1.0 μ L；
H) input mode: Splitless injecting samples, valve opening after 1.0min；
I) mode: EI is ionized；
J) mass scan range: 45u~550u；
K) ionizing energy: 70eV；
L) scanning mode: Salbutamol Selected Ion Monitoring；
M) solvent delay: 3.0min.
S1 is filtered with 0.45 μm of filter membrane.
Beneficial effects of the present invention: four major class common in plastic products, including 19 kinds of phthalic acids can be measured simultaneously
Esters, 7 kinds of adipic acid esters, 5 kinds of phosphoric acid esters, a kind of acetyl tributyl citrate esters amount to 34 kinds of plasticizer.It is more to be related to type, covers
Capping is wide, and application range is more extensive.
Ultrasonic extraction method is selected to extract a variety of plasticizer in plastic products, pre-processing device is at low cost, and method is easy to be fast
Speed, it is easy to spread universal；
Select ethyl acetate as Extraction solvent, toxicity is low, and the impure peak of solvent is few, and can obtain satisfied extraction
Effect.
Measuring method high sensitivity, can not only meet the limitation requirement of existing regulation, but also can be used as Chinese foreign skill
The technological reserve of art trade barrier.
Detailed description of the invention
The total ion current figure of 34 kinds of plasticizer standard solution of Fig. 1；
The GC/MS-SIM of 34 kinds of plasticizer standard solution of Fig. 2 schemes；
The GC/MS-SIM of Fig. 3 actual sample 1# schemes；
The GC/MS-SIM of Fig. 4 actual sample 2# schemes；
The GC/MS-SIM of Fig. 5 actual sample 3# schemes；
The GC/MS-SIM of Fig. 6 actual sample 4# schemes.
Specific embodiment
Embodiment:
- Fig. 2 refering to fig. 1, wherein 1:DMA；2:DEA；3:DMP；4:DEP；5:TBP；6:DIPP；7:DIBA；8:DALP；9:
DBA；10:DPRP；11:DIBP；12:DBP；13:DMOEP；14:DMPP；15:DEOEP；16:DAP；17:ATBC；18:BBOEA；
19:TDCPP；20:DHXP；21:BBP；22:DEHA；23:TPP；24:BBPA；25:TEHP；26:DBOEP；27:CDPP；28:
DCHP；29:DEHP；30:TOCP；31:DNOP；32:TPCP；33:DINP；34:DIDP；
1:DIBP in Fig. 3；2:DBP；3:DEHA；4:DEHP；5:DINP；
1:DIBP in Fig. 4；2:DBP；3:DEHP；
1:DIBP in Fig. 5；2:DBP；3:TPP；
1:DIBP in Fig. 6；2:DBP；3:DEHP；4:DINP.
In the embodiment of the present invention, measuring method specific steps of the present invention to four classes, 34 kinds of plasticizer in 1 plastic products of table
It is as follows:
1) reagent and material
In addition to particular/special requirement, it should use and analyze pure grade or the above reagent, 34 kinds of plasticizer purity >=98% in table 1, in table 2
Extraction solvent purity is pure grade of analysis or more.
2) preparation of standard reserving solution and working solution:
34 kinds of each 100.0mg of plasticizer standard items are accurately weighed respectively, are respectively placed in 100mL volumetric flask, with acetic acid second
Ester is diluted to scale, mixes, is configured to the standard reserving solution of 1.0g/L, stored refrigerated at 4 DEG C；Then, various increasings are accurately pipetted
Agent standard reserving solution 10mL is moulded into 100mL volumetric flask, with ethyl acetate constant volume, is configured to the hybrid standard deposit of 100mg/L
It is stored refrigerated at 4 DEG C of liquid；Finally, being diluted to 0.5 μ g/L, 10 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/ step by step with ethyl acetate
L, the hybrid standard working solution of 500 μ g/L series of concentrations.
3) sample treatment
5g~10g representative sample is taken, is shredded to 0.25cm*0.25cm hereinafter, mixing.Weigh 1.0g sample (essence
Really arrive 0.001g), it is placed in conical flask, 25mL ethyl acetate is added, ultrasound 30min, then shifts extract liquor at 45 DEG C
Into 50mL volumetric flask, residue is washed 3 times with a small amount of ethyl acetate, and combining extraction liquid is settled to 50mL.With 0.45 μm of filter membrane
Filtering, upper machine are to be measured.If testing concentration is excessively high in solution, then sample introduction again after appropriate dilution.
4) instrument is analyzed
It is separated and is identified using GC-MS analysis method, using quantified by external standard method；
The GC-MS analysis condition of instrument analysis is as follows:
A) chromatographic column: DB-5MS capillary column 30m*0.25mm*0.25*m or suitable person；
B) chromatogram column temperature:, keeping 1min by 90 DEG C of initial temperature, rises to 200 DEG C with 15 DEG C/min, retains 2min, then with 15
DEG C/min rises to 235 DEG C, retain 8min, then rise to 250 DEG C with 5 DEG C/min, keeps 2min, finally rise to 300 with 20 DEG C/min
DEG C, keep 7.3min；
C) injector temperature: 250 DEG C；
D) chromatography-mass spectroscopy interface temperature: 250 DEG C；
E) ion source temperature: 250 DEG C；
F) carrier gas: helium, purity >=99.999%；Flow velocity, 1.0mL/min；
G) sample volume: 1 μ L；
H) input mode: Splitless injecting samples, valve opening after 1.0min；
I) mode: EI is ionized；
J) mass scan range: 45u~550u；
K) ionizing energy: 70eV；
L) scanning mode: Salbutamol Selected Ion Monitoring；
Wherein, the qualitative confirmation of 34 kinds of plasticizer be under the instrument condition of setting, i.e., under GC-MS full scan mode, to
Selection quasi-molecular ions (± 0.2min) appearance at identical retention time of liquid and hybrid standard working solution is surveyed, and corresponding mass spectrum is broken
The mass-to-charge ratio of piece ion is consistent with hybrid standard working solution.The mass spectral analysis parameter of 34 kinds of plasticizer is shown in Table 2.34 kinds of plasticizer marks
The total ion current figure of quasi- solution is shown in that Fig. 1, GC/MS-SIM figure are shown in Fig. 2.
5) result calculates: carrying out regression analysis to its respective concentration with the selection ion peak areas of various plasticizer, obtains
Standard curve, working curve linearly dependent coefficient are greater than 0.99, and abscissa is plasticizer concentration, and ordinate is determining for each plasticizer
Measure ion peak areas；To treated, sample is measured, the selection ion peak areas of the various plasticizer measured, substitutes into standard
Curve acquires the content of various plasticizer in sample；
The present invention takes in blank sample plus calibration method carrys out the precision and the rate of recovery of measuring method, adds three respectively
The mixed mark of a concentration level, 9 Duplicate Samples tests of each horizontal progress, the results are shown in Table 3, the average recovery rate of 34 kinds of plasticizer is
81.92~95.65%, RSD are 2.76~7.08%.
The present invention adds the mixed mark of various concentration in bare substrate, is measured, and determines its linear relationship, 34 kinds of plasticising
Agent is listed in Table 4 below in 1.6-38112 μ g/L concentration range, linear coefficient r >=0.998, concrete condition.
The method that mark-on is tested in blank sample is taken to determine that the detection limit of method obtains under conditions of S/N=3
The detection of 34 kinds of plasticizer is limited to 0.1-200 μ g/kg, meets the limitation requirement of current various countries' rule and standard, concrete condition column
In table 4.
With above-mentioned detection method, 11 kinds of practical plastic products are tested, measures and the results are shown in Table 5.
Table 1 four class, 34 kinds of plasticizer
The mass spectral analysis parameter of 2 34 kinds of plasticizer of table
The range of linearity and detection limit of 4 34 kinds of plasticizer of table
5 actual sample testing result of table
In the description of this specification, the description of term " one embodiment " etc. means that the embodiment or example is combined to describe
Particular features, structures, materials, or characteristics be included at least one embodiment or example of the invention.In the present specification,
Schematic expression of the above terms are not necessarily referring to identical embodiment or example.Moreover, the specific features of description, knot
Structure, material or feature can be combined in any suitable manner in any one or more of the embodiments or examples.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of measuring method of four 34 kinds of plasticizer of class, which comprises the following steps:
S1 sample pre-treatments: being added Extraction solvent in plastic-like, and ultrasound, extract liquor is transferred in volumetric flask, and constant volume uses micropore
Filter membrane filtering, upper machine are to be measured；
The preparation of S2 standard reserving solution and working solution: weighing the standard items of four 34 kinds of plasticizer of class respectively, carries out single standard storage
The preparation of standby liquid；Secondly, pipetting single standard stock solution constant volume in volumetric flask respectively, the mixing of four 34 kinds of plasticizer of class is obtained
Standard Stock solutions；Finally, being configured to the hybrid standard with four 34 kinds of plasticizer of class of concentration gradient with organic solvent diluting
Working solution；
The analysis of S3 instrument: it is separated and is identified using GC-MS analysis method, using quantified by external standard method；
S4 result calculates: carrying out regression analysis to its respective concentration with the selection ion peak areas of various plasticizer, obtains standard
Curve, working curve linearly dependent coefficient are greater than 0.99, and abscissa is plasticizer concentration, ordinate be each plasticizer it is quantitative from
Sub- peak area；To treated, sample is measured, the selection ion peak areas of the various plasticizer measured, and it is bent to substitute into standard
Line acquires the content of various plasticizer in sample.
2. the measuring method of four classes, 34 kinds of plasticizer according to claim 1, which is characterized in that wherein 34 kinds of plasticizer
It is qualitative confirmation be under the instrument condition of setting, i.e., under GC-MS full scan mode, the selection of prepare liquid and hybrid standard working solution
Quasi-molecular ions (± 0.2min) at identical retention time occurs, and the mass-to-charge ratio and hybrid standard work of corresponding mass spectrometric fragment ion
It is consistent to make liquid.
3. the measuring method of four classes, 34 kinds of plasticizer according to claim 1, which is characterized in that wherein S1, before sample
The specific operation process of reason is as follows: taking 5g~10g sample, is shredded to 0.25cm*0.25cm hereinafter, mixing；Weigh 1.0g
Sample is placed in conical flask, and 25mL ethyl acetate is added, then extract liquor is transferred to 50mL and held by the ultrasound 30min at 45 DEG C
In measuring bottle, residue is washed 3 times with a small amount of ethyl acetate, and combining extraction liquid is settled to 50mL.
4. the measuring method of four classes, 34 kinds of plasticizer according to claim 1, which is characterized in that S2 Plays stock solution with
The process for preparation of working solution is as follows:
34 kinds of each 100.0mg of plasticizer standard items are accurately weighed respectively, are respectively placed in 100mL volumetric flask, it is dilute with ethyl acetate
It releases to scale, mixes, be configured to the standard reserving solution of 1.0g/L, it is stored refrigerated at 4 DEG C；Then, various plasticizer are accurately pipetted
Standard reserving solution 10mL, with ethyl acetate constant volume, is configured to 4 DEG C of hybrid standard stock solution of 100mg/L into 100mL volumetric flask
Under it is stored refrigerated；Finally, being diluted to 0.5 μ g/L, 10 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 500 step by step with ethyl acetate
The hybrid standard working solution of μ g/L series of concentrations.
5. the measuring method of four classes, 34 kinds of plasticizer according to claim 1, which is characterized in that the analysis of S3 Instrumental
GC-MS analysis condition is as follows:
A) chromatographic column: 30m*0.25mm*0.25 μm of DB-5MS capillary column or suitable person；
B) chromatogram column temperature:, keeping 1min by 90 DEG C of initial temperature, rises to 200 DEG C with 15 DEG C/min, retains 2min, then with 15 DEG C/
Min rises to 235 DEG C, retains 8min, then rise to 250 DEG C with 5 DEG C/min, keeps 2min, finally rise to 300 DEG C with 20 DEG C/min,
Keep 7.3min；
C) injector temperature: 250 DEG C；
D) chromatography-mass spectroscopy interface temperature: 250 DEG C；
E) ion source temperature: 250 DEG C；
F) carrier gas: helium, purity >=99.999%；Flow velocity, 1.0mL/min；
G) sample volume: 1.0 μ L；
H) input mode: Splitless injecting samples, valve opening after 1.0min；
I) mode: EI is ionized；
J) mass scan range: 45u~550u；
K) ionizing energy: 70eV；
L) scanning mode: Salbutamol Selected Ion Monitoring；
M) solvent delay: 3.0min.
6. the measuring method of four classes, 34 kinds of plasticizer according to claim 1, which is characterized in that 0.45 μm of filter membrane of S1
Filtering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811226016.9A CN109142608A (en) | 2018-10-22 | 2018-10-22 | A kind of measuring method of four classes, 34 kinds of plasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811226016.9A CN109142608A (en) | 2018-10-22 | 2018-10-22 | A kind of measuring method of four classes, 34 kinds of plasticizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109142608A true CN109142608A (en) | 2019-01-04 |
Family
ID=64808762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811226016.9A Pending CN109142608A (en) | 2018-10-22 | 2018-10-22 | A kind of measuring method of four classes, 34 kinds of plasticizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109142608A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110658278A (en) * | 2019-10-12 | 2020-01-07 | 深圳海关工业品检测技术中心 | Rapid detection and analysis method for plasticizer in textile |
| CN112326859A (en) * | 2020-10-27 | 2021-02-05 | 常州进出口工业及消费品安全检测中心 | Method for testing residual quantity of various non-phthalate plasticizers in PVC |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101858897A (en) * | 2010-07-05 | 2010-10-13 | 深圳出入境检验检疫局玩具检测技术中心 | Detection method of phthalate plasticizer |
| CN103645272A (en) * | 2013-12-23 | 2014-03-19 | 深圳出入境检验检疫局工业品检测技术中心 | Method for detecting high-boiling-point substances in industrial products |
| CN106519500A (en) * | 2016-11-09 | 2017-03-22 | 广东省汕头市质量计量监督检测所 | Standard substance for phthalic acid ester plasticizer measurement and preparation method of standard substance |
-
2018
- 2018-10-22 CN CN201811226016.9A patent/CN109142608A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101858897A (en) * | 2010-07-05 | 2010-10-13 | 深圳出入境检验检疫局玩具检测技术中心 | Detection method of phthalate plasticizer |
| CN103645272A (en) * | 2013-12-23 | 2014-03-19 | 深圳出入境检验检疫局工业品检测技术中心 | Method for detecting high-boiling-point substances in industrial products |
| CN106519500A (en) * | 2016-11-09 | 2017-03-22 | 广东省汕头市质量计量监督检测所 | Standard substance for phthalic acid ester plasticizer measurement and preparation method of standard substance |
Non-Patent Citations (4)
| Title |
|---|
| SORAYA GALMÁN GRAÍÑO ET AL.: "GC-MS Screening Analysis for the Identification of Potential Migrants in Plastic and Paper-Based Candy Wrappers", 《POLYMERS》 * |
| 张伟亚 等: "微波萃取气相色谱-质谱法测定塑料中的增塑剂", 《塑料科技》 * |
| 李晔 等: "气相色谱-质谱法同时测定饮水中的35种增塑剂", 《卫生研究》 * |
| 郭春海 等: "气相色谱-质谱法测定聚氯乙烯包装材料和食品模拟物中的46种增塑剂", 《色谱》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110658278A (en) * | 2019-10-12 | 2020-01-07 | 深圳海关工业品检测技术中心 | Rapid detection and analysis method for plasticizer in textile |
| CN112326859A (en) * | 2020-10-27 | 2021-02-05 | 常州进出口工业及消费品安全检测中心 | Method for testing residual quantity of various non-phthalate plasticizers in PVC |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112903884B (en) | Method for simultaneously detecting phthalate compounds and metabolites thereof and application thereof | |
| Sabaredzovic et al. | Determination of 12 urinary phthalate metabolites in Norwegian pregnant women by core–shell high performance liquid chromatography with on-line solid-phase extraction, column switching and tandem mass spectrometry | |
| Dirven et al. | Metabolites of the plasticizer di (2-ethylhexyl) phthalate in urine samples of workers in polyvinylchloride processing industries | |
| KR101490179B1 (en) | Method for simultaneous analysis of phthalate components using hplc and mass spectrometry | |
| CN109142608A (en) | A kind of measuring method of four classes, 34 kinds of plasticizer | |
| Rastogi | Gas chromatographic analysis of phthalate esters in plastic toys | |
| CN106832881A (en) | Phthalic ester plasticizer and phosphorus flame retardant standard sample and sample preparation methods in polyurethane | |
| CN101482505A (en) | Method for fast detecting phthalate compound in plastic products | |
| CN105891374A (en) | Detection method for measuring eight preservatives in reconstituted tobaccos simultaneously | |
| Di Napoli-Davis et al. | Quantitation of tetrabromobisphenol-A from dust sampled on consumer electronics by dispersed liquid-liquid microextraction | |
| CN112684030A (en) | Method for detecting perfluoroalkanoic acid compound in aquatic product by enrichment purification-liquid chromatography tandem mass spectrometry and application | |
| CN111175412A (en) | Method for detecting 16 phthalate plasticizers in children products | |
| CN110530705A (en) | A kind of pork place of production source tracing method based on mineral element fingerprint | |
| CN103760290B (en) | The assay method of transfer volume of epoxy chloropropane in food contact material | |
| CN105319296A (en) | Measuring method for methyl alcohol content | |
| Idoine et al. | Bulk and compound‐specific isotopic characterisation of illicit heroin and cling film | |
| CN105738511B (en) | A kind of method of 1,2- phthalic acids-dialkyl esters plasticizer in gas chromatography-mass spectrography detection plastics | |
| CN104076104A (en) | Method for detecting transfer volume of phosphate ester plasticisers in acid sweat in textile | |
| DE60307836T2 (en) | FLOW ENZYMASSAY USING A MASS SPECTROMETRIC DETECTION | |
| EP0190766B1 (en) | Determination of prokallikrein | |
| CN102519947A (en) | Method for detecting trace copper in wastewater rapidly | |
| CN110108829A (en) | A kind of method of furans benzene olefin(e) acid sodium residual quantity in detection aquatic products | |
| CN109633021B (en) | Method for detecting additive in sufentanil medicine | |
| CN102175811B (en) | Method for identifying purity of lecithin | |
| CN101936970B (en) | Method for determining acrylic ester compound in polypropylene fiber rubber used for cigarette |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190104 |
|
| RJ01 | Rejection of invention patent application after publication |