CN106770820A - Three kinds of detection methods of phosphorus flame retardant in a kind of polyurethane foam product - Google Patents
Three kinds of detection methods of phosphorus flame retardant in a kind of polyurethane foam product Download PDFInfo
- Publication number
- CN106770820A CN106770820A CN201611138578.9A CN201611138578A CN106770820A CN 106770820 A CN106770820 A CN 106770820A CN 201611138578 A CN201611138578 A CN 201611138578A CN 106770820 A CN106770820 A CN 106770820A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- polyurethane foam
- phosphorus flame
- kinds
- foam product
- 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
- G01N30/04—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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention belongs to electronic technology field, three kinds of detection methods of phosphorus flame retardant in specifically related to a kind of polyurethane foam product, detection object is phosphorus flame retardant tricresyl phosphate (propyl group of 1 chlorine 2) ester (TCPP), three (2 chloroethyl) phosphates (TCEP) and tricresyl phosphate (2,3 two chloropropyl) ester (TDCPP)；Under certain temperature and time, using organic solvent ultrasonic extraction, GC-MS is determined.The sensitivity of the method for the invention, the rate of recovery are high, and the precision of measurement result is good.
Description
First, technical field
The invention belongs to electric detective technology field, and in particular to 3 kinds of disabling phosphorus systems resistance in a kind of polyurethane foam product
Fire the detection method of agent.
2nd, technical background
In recent years, the demand to fire retardant is increasing, and phosphorus flame retardant is widely used, and efficiency is higher, but it has life
Thing cumulative bad, being contacted with phosphonium flame retardant can have adverse effect on for a long time to human body, such as function of immune system deterioration, system genitale
It is system obstacle, memory loss, even carcinogenic etc..
There are the fire-retardant aspect regulation or standard of this country in current many countries, and such as UL standards (mark by U.S. insurance industry research institute
It is accurate), ASTM standard (ASTM standard), CSA standards (Canadian industrial standard association criterion), JIS standard (days
This industrial standard), DIN standards (DIN), BS standards (British Standard), and iso standard (ISO standards)
Deng.
The flame retardant regulation and standard of China are also gradually improved, and Chinese and EU prohibits the use of tricresyl phosphate-(2- chlorine isopropyls
Base) ester (TCPP), tricresyl phosphate (2,3- bis- chloropropyl) ester (TDCPP), tricresyl phosphate-(2- chloroethyls) ester (TCEP).
At present, the pretreatment technology set up for phosphorus flame retardant, detection method are varied.Wherein, ultrasonic wave
Abstraction technique is widely adopted because its extraction efficiency is high, extraction time is short, Extracting temperature is low and the characteristics of wide adaptability.Such as
Sample pre-treatments [Fang Jie, Wang Xiaoning, Li Qing are carried out using acetone and the ultrasonic extraction of n-hexane mixed solvent.Gas chromatography mass spectrometry method is surveyed
Determine to limit the use of bromine system and phosphorus flame retardant Beijing Institute of Clothing Tech journal, 2010,30 (2) in textile：61-65], using gas phase color
Spectrum-mass spectrometric hyphenated technique establishes the gas chromatography-mass spectrum of the phosphorus tolyl phosphate (TOCP) of phosphorus flame retardant three in textile
(GC-MS) it is combined detection method.It is extractant ultrasonic extraction low-polarity components using chloroform-n-hexane (volume ratio is 1: 1)
Establish detection method [Chen Yuan, the Chen Lieqiang, yellow Hua Jie of fire retardant.GC-MS quick detection bromo-derivative hinders
Combustion agent environmental protective chemical industries, 2009,29 (1)：89-93].Utilize with toluene as Extraction solvent, it is many in ultrasonic extraction electronic and electrical equipment
Bromo biphenyl and PBDE establish gas chromatography-mass spectrography and determine PBBs (PBBs) and many bromines connection in plastic product
Phenylate (PBDEs) method [Li Wei, Lu Chunshan, Li Kang, etc..Brominated flame retardant in gas chromatography-mass spectrography detection plastic product
Agent [J] analytical chemistry, 2009,37 (9)：1319-1323].
However, for the phosphorus flame retardant tricresyl phosphate in polyurethane (PU) foam-(2- chloro isopropyls) ester (TCPP), phosphoric acid
Three (2,3- bis- chloropropyl) esters (TDCPP), the detection method of tricresyl phosphate-(2- chloroethyls) ester (TCEP) does not find.
Patent of the present invention provides a kind of method for detecting the content containing phosphorus flame retardant in polyurethane foam product, can
Meet the phosphorus flame retardant detection demand of polyurethane foam product.
3rd, the content of the invention
The purpose of the present invention is choosing suitable solvent dissolution extraction, so as to obtain a kind of detection method of optimization.
The technical solution adopted by the present invention：Tetrahydrofuran, dimethylbenzene, DMF (DMF) etc. are tested respectively
Solvent extracts polyurethane foam, again with toluene constant volume, by Gas chromatographyMass spectrometry, the rate of recovery of determination sample.
Result finds that DMF does Extraction solvent best results.
Experiment comprises the following steps
A () takes representational polyurethane foam sample, cut to 3mm × below 3mm；Weigh a certain amount of treated foam
Sample is in conical flask with cover；
B () accurately pipettes 20mL and extracts organic solvent in above-mentioned conical flask；
C conical flask is put into 1h in 60 DEG C of ultrasonic cleaner by ()；
D () adds toluene constant volume；
E () takes supernatant after solution vibration is fully mixed by the way of centrifugation or filtering, treat that GC-MS is analyzed.
The gaschromatographic mass spectrometry condition is：
Carrier gas：Helium；
Chromatographic column：DB-35MS, length 30m, internal diameter 0.25mm, 0.25 μm of film thickness；
Sampling system：Automatic sampler；
Injector temperature：250℃；
Sample size：1μL；
100 DEG C of column temperature has kept 2min, and then 30 DEG C/min is warming up to 300 DEG C of holding 3min；
Column flow：1.1mL/min
Mass Spectrometry Conditions：230 DEG C of ion source temperature, SIM modes are scanned.
The object of detection is tricresyl phosphate (the chloro- 2- propyl group of 1-) ester, three (2- chloroethyls) phosphates and tricresyl phosphate (2,3- bis-
Chloropropyl) ester.
It is qualitative according to retention time, and quantified using external standard peak area method.Qualitative, quota ion see the table below：
| Compound name | Retention time (min) | Quota ion | Qualitative ion |
| TCPP | 7.550 | 99 | 125,157,277 |
| TCEP | 7.660 | 249 | 63,99,143 |
| TDCPP | 9.468 | 75 | 99,191,381 |
Beneficial effect：3 kinds of phosphorus flame retardants are detected using this technology route, with being simple to operate and friendly to environment, extract
The advantages of efficiency high.Additionally, the present invention is only for polyurethane foam sample, it is with strong points.It is all using extractant in the present invention
The less reagent of toxicity, is adapted to daily extensive sample detection.The present invention for the detection of phosphorus flame retardant can reach compared with
Low detection limit, the result of the rate of recovery is satisfactory, relative deviation ＜ 10%, can meet routine testing.
Brief description of the drawings
Fig. 1 tricresyl phosphates-(2- chloro isopropyls) ester (TCPP), tricresyl phosphate (2,3- bis- chloropropyl) ester (TDCPP), tricresyl phosphate-
(2- chloroethyls) ester (TCEP) standard gas chromatograph mass spectrogram (total ion current figure)
The standard mass spectrogram of Fig. 2 TCPP
The standard mass spectrogram of Fig. 3 TCEP
The standard mass spectrogram of Fig. 4 TDCPP
Specific implementation method
Below in conjunction with specific embodiment, the present invention is expanded on further.These embodiments be merely to illustrate the present invention and without
In limitation the scope of the present invention.The test method of unreceipted actual conditions in the following example, generally according to normal condition or presses
According to the condition proposed by manufacturer.Unless otherwise defined, all specialties used in text are ripe with this area with scientific words
Practice meaning familiar to personnel institute identical.Additionally, any method similar to described content or impartial and material all can be used for this
In invention, the preferable implementation described in text only presents a demonstration and is used.
Embodiment 1
1st, instrument and reagent
Gas chromatograph：Agilent MSD5975-GC7890 GC-MSs
Standard substance：Tricresyl phosphate-(2- chloro isopropyls) ester (TCPP), tricresyl phosphate-(2,3- dibromopropyl) -ester (TDCPP),
Tricresyl phosphate-(2- chloroethyls) ester (TCEP).
DMF：Analysis is pure
Toluene：Analysis is pure
2nd, instrumental conditions
Capillary chromatographic column：DB-35MS 30m×0.25mm×0.25μm
Heating schedule：100 DEG C of initial temperature, keeps 2min, is then warmed up to 300 DEG C with the speed of 30 DEG C/min, keeps
3min。
Injector temperature：250℃；
Ion source temperature：230℃；
Carrier gas：Helium
Column flow：1.1mL/min
Split ratio：Do not shunt
3rd, pre-treatment scheme：Typical sample is done using polyurethane foam on the market, it is processed.
Take a certain amount of representative sample, cut to 3mm × below 3mm (that cuts is smaller, is more conducive to dissolving).Weigh 1g
(being accurate to 0.0001g) adds 20mL DMF, covered and enclosed to be put into 60 DEG C of ultrasonic cleaners in vial, makes its molten
Solution, can be accelerated to dissolve, extraction time 1h with forced oscillation halfway.
4th, at a certain temperature, vibrated with vortex oscillator with toluene constant volume to 25mL in above-mentioned solution, stand several points
Zhong Hou, supernatant is filtered with 0.45 μm of polytetrafluoroethylene (PTFE) filter, treats that GC-MS is analyzed.As liquid is muddy, centrifugal treating can be used
Afterwards, then supernatant is taken.
5th, it is qualitative according to retention time, and quantified using external standard peak area method.Qualitative, quota ion see the table below：
| Compound name | Retention time (min) | Quota ion | Qualitative ion |
| TCPP | 7.550 | 99 | 125,157,277 |
| TCEP | 7.660 | 249 | 63,99,143 |
| TDCPP | 9.468 | 75 | 99,191,381 |
Carry out the experiment of linear equation, precision, the rate of recovery and detection limit again with this understanding.
6th, linear equation and standard items chromatogram
Standard reserving solution：TCPP is separately added into 100mL volumetric flasks, the standard items of TCEP, TDCPP are appropriate, use toluene
It is settled to scale.
Standard working curve is prepared with above-mentioned standard liquid：Take standard reserving solution appropriate, be configured to concentration for 1~20 μ g/
ML or so series standard working solutions, take above-mentioned series standard working solution in sample injection bottle, under above-mentioned chromatographic condition respectively
It is measured, with peak area y as ordinate, concentration x carries out linear regression for abscissa, as a result such as table 1：
1 three kinds of retention times of phosphorus flame retardant of table, linear equation and coefficient correlation
7th, precision
Sample after crushing is taken, mark-on experiment is carried out, sample pre-treatments are carried out according to above-mentioned steps, do the precision reality of sample
Test (n=6).Experimental result is as shown in table 2：
The Precision Experiment (n=6) of the sample of table 2
| Compound | Average value (mg/kg) | Relative standard deviation (%) |
| TCPP | 137.6 | 3.9 |
| TCEP | 111.2 | 3.0 |
| TDCPP | 125.9 | 3.4 |
8th, method recovery of standard addition experiment
The recovery of standard addition experimental result of this method is as shown in table 3：
The recovery test result of table 3
The average recovery rate of TCPP is 94.8%, RSD% for the average recovery rate of 3.0%TCEP is 101.8%, RSD%
For 7.7%TDCPP average recovery rate for 96.5%, RSD% be 2.2%
7th, test limit
According to three times signal to noise ratio, TCPP is drawn, the detection of TCEP, TDCPP method is limited to：20mg/kg, disclosure satisfy that daily inspection
The need for survey.
Claims (4)
1. a kind of three kinds of detection methods of phosphorus flame retardant in polyurethane foam product, its feature is comprised the following steps：Take certain
The representative sample of amount, weighs 1g (being accurate to 0.0001g) in glass spinner flask after crushing, add 20mL organic solutions extraction
Take, at 60 DEG C, be put into dissolving and extraction in ultrasonic cleaner, 1 hour extraction time, after being cooled to room temperature, add toluene
Constant volume filters extract solution with 0.45 μm of filter of polytetrafluoroethylene (PTFE) filter, with machine on gas chromatography mass spectrometer device to 25mL
Analyze, the gaschromatographic mass spectrometry condition is：
Carrier gas：Helium；
Chromatographic column：DB-35MS, length 30m, internal diameter 0.25mm, 0.25 μm of film thickness；
Sampling system：Automatic sampler；
Injector temperature：250℃；
Sample size：1μL；
100 DEG C of column temperature has kept 2min, and then 30 DEG C/min is warming up to 300 DEG C of holding 3min；
Column flow：1.1mL/min
Mass Spectrometry Conditions：230 DEG C of ion source temperature, SIM modes are scanned.
2. three kinds of detection methods of phosphorus flame retardant in a kind of polyurethane foam product according to claim 1, detection
Object is tricresyl phosphate (the chloro- 2- propyl group of 1-) ester, three (2- chloroethyls) phosphates and tricresyl phosphate (2,3- bis- chloropropyl) ester.
3. three kinds of detection methods of phosphorus flame retardant, its feature in a kind of polyurethane foam product according to claim 1
It is that described foam product type is polyurethane foam.
4. three kinds of detection methods of phosphorus flame retardant, its feature in a kind of polyurethane foam product according to claim 1
It is that extraction organic solvent used is DMF.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611138578.9A CN106770820A (en) | 2016-12-12 | 2016-12-12 | Three kinds of detection methods of phosphorus flame retardant in a kind of polyurethane foam product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611138578.9A CN106770820A (en) | 2016-12-12 | 2016-12-12 | Three kinds of detection methods of phosphorus flame retardant in a kind of polyurethane foam product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106770820A true CN106770820A (en) | 2017-05-31 |
Family
ID=58875461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611138578.9A Pending CN106770820A (en) | 2016-12-12 | 2016-12-12 | Three kinds of detection methods of phosphorus flame retardant in a kind of polyurethane foam product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106770820A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107290449A (en) * | 2017-06-15 | 2017-10-24 | 深圳职业技术学院 | Three in a kind of textile（2 chloroethyls）The quick selective mechanisms method of phosphate |
| CN108195981A (en) * | 2017-11-16 | 2018-06-22 | 吉贵祥 | The method for quantitatively detecting tricresyl phosphate (bis- chloro- 2- propyl of 1,3-) ester in Fine Particles PM2.5 |
| CN110702823A (en) * | 2019-11-12 | 2020-01-17 | 东莞市中鼎检测技术有限公司 | Method for efficiently extracting organic matters in textiles and similar materials |
| CN114624118A (en) * | 2022-05-17 | 2022-06-14 | 江苏金旺新材料科技有限公司 | Dynamic detection device and detection method for performance of foam adhesive tape |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101216467A (en) * | 2008-01-14 | 2008-07-09 | 谱尼测试科技（北京）有限公司 | Electronic material hexabromocyclododecane content determination method |
| CN103616469A (en) * | 2013-12-13 | 2014-03-05 | 中华人民共和国北京出入境检验检疫局 | Method for detecting organophosphate flame retardant |
| CN104391069A (en) * | 2014-11-27 | 2015-03-04 | 广州广电计量检测股份有限公司 | Method for simultaneously detecting multiple phosphorus-based flame retardants in plastics |
| CN104931638A (en) * | 2015-07-01 | 2015-09-23 | 必维申优质量技术服务江苏有限公司 | Detection method of TCEP and TCPP in textile, leather and plastics |
-
2016
- 2016-12-12 CN CN201611138578.9A patent/CN106770820A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101216467A (en) * | 2008-01-14 | 2008-07-09 | 谱尼测试科技（北京）有限公司 | Electronic material hexabromocyclododecane content determination method |
| CN103616469A (en) * | 2013-12-13 | 2014-03-05 | 中华人民共和国北京出入境检验检疫局 | Method for detecting organophosphate flame retardant |
| CN104391069A (en) * | 2014-11-27 | 2015-03-04 | 广州广电计量检测股份有限公司 | Method for simultaneously detecting multiple phosphorus-based flame retardants in plastics |
| CN104931638A (en) * | 2015-07-01 | 2015-09-23 | 必维申优质量技术服务江苏有限公司 | Detection method of TCEP and TCPP in textile, leather and plastics |
Non-Patent Citations (5)
| Title |
|---|
| 丁浩: "《塑料工业实用手册 第二版 上册》", 31 August 2000, 化学工业出版社 * |
| 熊腊森: "《粘接手册》", 31 July 2008, 机械工业出版社 * |
| 王成云等: "超声萃取/气相色谱-串联质谱法同时测定纺织品中6种禁用有机磷阻燃剂", 《分析测试学报》 * |
| 陶琳等: "气相色谱-质谱法测定聚氨酯泡沫中3中阻燃剂", 《理化检验（化学分册）》 * |
| 黎厚斌: "《包装应用化学》", 31 January 2014, 印刷工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107290449A (en) * | 2017-06-15 | 2017-10-24 | 深圳职业技术学院 | Three in a kind of textile（2 chloroethyls）The quick selective mechanisms method of phosphate |
| CN107290449B (en) * | 2017-06-15 | 2020-09-18 | 深圳职业技术学院 | Rapid screening and detecting method for tris (2-chloroethyl) phosphate in textile |
| CN108195981A (en) * | 2017-11-16 | 2018-06-22 | 吉贵祥 | The method for quantitatively detecting tricresyl phosphate (bis- chloro- 2- propyl of 1,3-) ester in Fine Particles PM2.5 |
| CN110702823A (en) * | 2019-11-12 | 2020-01-17 | 东莞市中鼎检测技术有限公司 | Method for efficiently extracting organic matters in textiles and similar materials |
| CN114624118A (en) * | 2022-05-17 | 2022-06-14 | 江苏金旺新材料科技有限公司 | Dynamic detection device and detection method for performance of foam adhesive tape |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106770820A (en) | Three kinds of detection methods of phosphorus flame retardant in a kind of polyurethane foam product | |
| CN103235062B (en) | Detecting method for multiple kinds of poly brominated diphenyl ethers in aquatic product | |
| CN102662020B (en) | GC-MS detection method for phosphate ester flame retardant plasticizers in textiles | |
| CN102628843B (en) | Gas chromatography for detection of phosphate fire-retardant plasticizer in textile | |
| JP5859011B2 (en) | Extraction method and system for monitoring the presence of phosphate esters in jet fuel | |
| CN103149309A (en) | Measuring method for the furfural content of transformer oil | |
| CN104391069B (en) | A kind of method of multiple phosphorus flame retardant in plastics of detection simultaneously | |
| CN103616458A (en) | Method for quantitatively detecting six kinds of nitrobenzene compounds in fine atmospheric particles PM2.5 | |
| CN103713069A (en) | Method for measuring polyvinyl chloride content in plastic through thermal cracking-gas chromatography mass spectrometry | |
| CN108872415A (en) | The analyzing detecting method of monohydroxy polycyclic aromatic hydrocarbon in a kind of urine | |
| CN108469482B (en) | Method for simultaneously determining phosphorus flame retardant and bromine flame retardant in PVC (polyvinyl chloride) by GC-MS (gas chromatography-Mass spectrometer) | |
| CN102998382B (en) | Method for measuring contents of methanol, sec-butyl alcohol, sesamol and musk xylene in additive for cigarette | |
| CN103308641A (en) | High performance liquid chromatography-tandem mass spectrometry measuring method of three amide herbicides in tobacco and tobacco products | |
| CN102323342B (en) | Detecting method of aromatic amine compound in water sample | |
| CN106053681A (en) | Pretreatment method for ambient air or exhaust gas sample and determination method for dioxin | |
| CN105467054B (en) | The method that ultra-performance liquid chromatography determines PBBs and PBDE based flame retardant in textile | |
| CN102288690A (en) | Method for determining content of tri (2-chloroethyl) phosphate | |
| CN103123346A (en) | Rapid instrumental analysis method for zearalenone in food | |
| CN105467043B (en) | A method of measuring 1,6 hexanediol diacrylate content | |
| CN102759593A (en) | Chromatograph detection method for inorganic anions and cations in DOPO | |
| CN102243221B (en) | Detection method for special fire retardant content in textile | |
| Odell et al. | A ‘cold synthesis’ of heroin and implications in heroin signature analysis: Utility of trifluoroacetic/acetic anhydride in the acetylation of morphine | |
| CN105203656A (en) | Shandong area insulator dirtiness water-soluble negative ion ingredient testing method | |
| CN103926363A (en) | Gas chromatography/mass spectrometry (GC/MS) method for detecting dimethyl fumarate in food additive | |
| CN104237437A (en) | Gas chromatography detection method of p-xylylene dichloride |
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: 20170531 |
|
| RJ01 | Rejection of invention patent application after publication |