CN106526006A - Method for detecting volatiles residue in hot-melt adhesive for cigarettes - Google Patents

Method for detecting volatiles residue in hot-melt adhesive for cigarettes Download PDF

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Publication number
CN106526006A
CN106526006A CN201610935669.9A CN201610935669A CN106526006A CN 106526006 A CN106526006 A CN 106526006A CN 201610935669 A CN201610935669 A CN 201610935669A CN 106526006 A CN106526006 A CN 106526006A
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China
Prior art keywords
sample
temperature
isopropanol
acetone
methyl acetate
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CN201610935669.9A
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Chinese (zh)
Inventor
邵兴伟
吴昭
谭烨
刘吟
彭建
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China Tobacco Hunan Industrial Co Ltd
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China Tobacco Hunan Industrial Co Ltd
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Priority to CN201610935669.9A priority Critical patent/CN106526006A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N2030/042Standards

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  • 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)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

The invention provides a method for detecting volatiles residue in hot-melt adhesive for cigarettes; the method comprises the steps of (1) preparing a standard working solution for various volatiles; (2) preparing a sample; (3) determining by headspace-gas chromatography/mass spectrometry process; (4) calculating measurement results for various volatiles in the sample. The method is simple and convenient, and ingredient loss due to complex pre-treatment is avoided; dimethyl formamide is selected as a matrix corrective, matrix effect can be relieved, all volatiles to be detected can be dissolved, and the ingredients to be detected can also be detected without influence; the method has the advantages of good operation accuracy, high sensitivity and good repeatability.

Description

The detection method of volatile ingredient residual in a kind of hot-melt adhesive for cigarette
Technical field
The invention belongs to Tobacco Analysis technical field, and in particular to the inspection of volatile ingredient residual in a kind of hot-melt adhesive for cigarette Survey method.
Background technology
In hot-melt adhesive for cigarette volatile ingredient residual, be it is introduced by raw material itself, mainly residual monomer with have Machine solvent.Hot-melt adhesive for cigarette operating temperature is high, and step is applied under molten condition, is cooled to solid-state and completes to be glued, produces under molten condition Raw volatile ingredient residual is gathered in cigarette filter, is produced bad smell, is affected cigarette odor-absorbing, reduces cigarette quality. Secondly, the volatile ingredient such as middle acetone, isopropanol, methyl acetate has larger harm, the safety one of smoking material to human body It is directly tobacco business focus of attention.Therefore, carry out for volatile ingredient residual in hot-melt adhesive for cigarette effective, quick, accurate Analyzing detecting method, to ensure cigarette product quality and safety have important meaning.Water base adhesive, glyceryl triacetate and gluing In the samples such as agent, the assay method of volatility residual has document report, and said method is not suitable for the hot melt of heating and melting feature The detection of volatile ingredient residual in glue.
At present, static headspace-GC-MS fado is used for the measure of volatility residual in cigarette packaging material, so far also not See the report detected with static headspace-GC-MS in PUR.
The content of the invention
For above-mentioned the deficiencies in the prior art, the characteristics of the purpose of the present invention is for hot-melt adhesive for cigarette, there is provided Yi Zhongneng Quickly, accurately, the method that batch detection goes out the volatile ingredients such as hot-melt adhesive for cigarette acetone, isopropanol, methyl acetate.
The technical scheme that the present invention is provided:The detection method of volatile ingredient residual in a kind of hot-melt adhesive for cigarette, including such as Lower step:
(1) preparation of standard working solution:Acetone, isopropanol and methyl acetate standard substance are weighed, with chromatographically pure dimethyl Methanamide is substrate correction agent solvent, and Jing stepwise dilutions are configured to hybrid standard working solution;
(2) preparation of sample:PUR is shredded, 0.2000g is weighed and is placed in ml headspace bottle, accurately add 2mL dimethyl Methanamide, is sealed to be measured immediately;
(3) HS GC mass spectrometric determination:Sample and standard substance are put in Static Headspace instrument and are processed, condition is: Sample bottle equilibrium temperature:120 DEG C, sample loop temperature:140 DEG C, transmission line temperature:180℃;Sample bottle equilibration time 45min is low Fast concussion pattern;Sample bottle moulding pressure 138kpa, pressing time 0.20min;Inflationtime:0.20min;Sample loop volume 3.0mL, sample loop equilibration time 0.05min;Sample injection time 1.0min;By sample and standard substance Jing after head space process, pass through Gas chromatographyMass spectrometry is measured to acetone, isopropanol and methyl acetate;
(4) in sample various volatile ingredient measurement results calculating:According to the measurement result of standard working solution, with third The peak area of ketone, isopropanol and methyl acetate distinguishes drawing curve to mass concentration, obtains standard working curve, then by sample Detect in product that the peak area of acetone, isopropanol and methyl acetate substitutes into standard working curve respectively, obtains acetone, isopropanol in sample With the content of methyl acetate.
Further, in the step (3), the condition of gas chromatogram is:Innowax fused quartz capillary chromatography posts (30m×0.25mm×0.25μm);Injector temperature:250℃;Temperature programming:50 DEG C of initial temperature, keep 2min, with 4 DEG C/ Min rises to 200 DEG C, keeps 10min;Split sampling, split ratio 10:1;Carrier gas:Helium (purity is 99.999%);Constant current mould Formula, flow velocity are 2.0mL/min;Sample size:1μL.
Further, in the step (3), mass spectrographic condition is:EI ionizes pattern, ionization energy 70eV;Ion source temperature: 230℃;Transmission line temperature:250℃;150 DEG C of level Four bar temperature;Scanning of the mass spectrum mode:Full scan (SCAN), sweep limitss 30~ 350amu。
Further, in step (1) the hybrid standard working solution acetone, isopropanol and methyl acetate mass concentration It is:1mg/L、2mg/L、4mg/L、8mg/L、16mg/L.
The method of the present invention for PUR operating temperature the characteristics of 100 DEG C -120 DEG C, compared with prior art this Bright method has following excellent results:
(1) present invention optimizes head space equilibrium temperature, PUR is made to be maintained at molten condition, actual response PUR work Make the volatilization situation of 3 kinds of compositions such as acetone under state, isopropanol and methyl acetate, method is simple and convenient, it is to avoid complicated front place Manage and caused ingredients from lossing;In the samples such as water base adhesive, glyceryl triacetate and adhesive, the assay method of volatility residual is put down Weighing apparatus temperature is relatively low, is not suitable for the detection of volatile ingredient residual in the PUR of heating and melting feature;And formaldehyde in PUR, The object of the assay method such as benzene and benzene homologues, phenols polyphenoils analysis is different, is not suitable for acetone, isopropanol and acetic acid first The detection of 3 kinds of volatility residuals such as ester.
(2) dimethylformamide is chosen as substrate correction agent, can reduce matrix effect and dissolve all to be measured waving The property sent out composition can not disturb the detection of composition to be measured again.
(3) qualitative and detection by quantitative is carried out simultaneously using mass detector, it is to avoid the false positive being likely to occur.
(4) the inventive method has the advantages that to operate accurate, sensitivity high and reproducible.The detection of acetone is limited to 0.05mg/L, is quantitatively limited to 0.15mg/L, and relative standard deviation is 1.47%, and the response rate is between 95.1~102.3%;Isopropyl The detection of alcohol is limited to 0.06mg/L, is quantitatively limited to 0.19mg/L, and relative standard deviation is 2.17%, the response rate 94.8~ Between 99.2%;The detection of methyl acetate is limited to 0.10mg/L, is quantitatively limited to 0.35mg/L, and relative standard deviation is 3.44%, The response rate is between 92.4~98.6%.
Description of the drawings
Fig. 1 is the standard working curve of acetone;
Fig. 2 is the standard working curve of isopropanol;
Fig. 3 is the standard working curve of methyl acetate;
Fig. 4 is the gas chromatogram of hot-melt adhesive for cigarette sample A;
Fig. 5 is the gas chromatogram of hot-melt adhesive for cigarette sample B.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
0.0500g acetone, isopropanol and methyl acetate standard substance are weighed respectively, are placed in 1000mL volumetric flasks, are used chromatograph Absolute dimethylformamide is settled to scale, and the solution is hybrid standard storing solution.Accurately pipette 2mL, 4mL, 8mL, 16mL, The 32mL hybrid standard storing solutions, are respectively placed in 100mL volumetric flasks, are settled to scale with chromatograph absolute dimethylformamide, i.e., Obtain series standard working solution.The serial mixed standard solution concentration of preparation is:1mg/L、2mg/L、4mg/L、8mg/L、16mg/ L。
PUR sample A is shredded, 0.2000g is weighed and is placed in ml headspace bottle, accurately add 2mL dimethylformamides, Jing HS GC mass spectrograph is analyzed, and head space condition is:Sample bottle equilibrium temperature:120 DEG C, sample loop temperature:140 DEG C, Transmission line temperature:180℃;Sample bottle equilibration time 45min, low speed concussion pattern;Sample bottle moulding pressure 138kpa, during pressurization Between 0.20min;Inflationtime:0.20min;Sample loop volume 3.0mL, sample loop equilibration time 0.05min;Sample injection time 1.0min.GC conditions are:Innowax fused quartz capillary chromatography posts (30m × 0.32mm × 0.25 μm);Injection port Temperature:250℃;Temperature programming:50 DEG C of initial temperature, keeps 2min, rises to 200 DEG C with 4 DEG C/min, keeps 10min;It is diverted into Sample, split ratio 10:1;Carrier gas:Helium (purity is 99.999%);Constant current mode, flow velocity are 2.0mL/min;Sample size:1μL. Mass Spectrometry Conditions are:EI ionizes pattern, ionization energy 70eV;Ion source temperature:230℃;Transmission line temperature:250℃;Level Four bar temperature 150℃;Scanning of the mass spectrum mode:Full scan (SCAN), 30~350amu of sweep limitss.
Every grade of standard solution parallel assay 2 times, averages.The peak area of each component is bent to mass concentration drawing Line, standard working curve of the accompanying drawing 1 for acetone, standard working curve of the accompanying drawing 2 for isopropanol, mark of the accompanying drawing 3 for methyl acetate Quasi- working curve, accompanying drawing 4 are hot-melt adhesive for cigarette sample A chromatograms, and each volatile ingredient standard working curve is as shown in table 1:
1 each volatile ingredient standard working curve of table
By the acetone in the sample A measured under the same terms, isopropanol and methyl acetate chromatographic peak area, standard work is substituted into Make curve, try to achieve the content of the acetone, isopropanol and methyl acetate in sample.Sample determination twice, is averaged, and tries to achieve sample In A, content of acetone is 15.66mg/L, and isopropanol content is 7.66mg/L, and methyl acetate content is 5.20mg/L.
Embodiment 2
As described in Example 1, another PUR sample B is selected, accompanying drawing 5 is hot-melt adhesive for cigarette sample B chromatograms.Sample is surveyed Fixed to average twice, it is 12.94mg/L to try to achieve content of acetone in sample B, and isopropanol content is 7.78mg/L, methyl acetate Content is 9.33mg/L.
The detailed description of specific embodiments of the present invention is the foregoing is only, the present invention is not limited with this, it is all at this Any modification, equivalent and improvement for being made in the mentality of designing of invention etc., should be included in protection scope of the present invention it It is interior.

Claims (4)

1. the detection method that volatile ingredient is remained in a kind of hot-melt adhesive for cigarette, it is characterised in that comprise the steps:
(1) preparation of standard working solution:Acetone, isopropanol and methyl acetate standard substance are weighed, with chromatographically pure dimethyl formyl Amine is substrate correction agent solvent, and Jing stepwise dilutions are configured to hybrid standard working solution;
(2) preparation of sample:PUR is shredded, 0.2000g is weighed and is placed in ml headspace bottle, accurately add 2mL dimethyl formyls Amine, is sealed to be measured immediately;
(3) HS GC mass spectrometric determination:Sample and standard substance are put in Static Headspace instrument and are processed, condition is:Sample Bottle equilibrium temperature:120 DEG C, sample loop temperature:140 DEG C, transmission line temperature:180℃;Sample bottle equilibration time 45min, low speed shake Swing pattern;Sample bottle moulding pressure 138kpa, pressing time 0.20min;Inflationtime:0.20min;Sample loop volume 3.0mL, Sample loop equilibration time 0.05min;Sample injection time 1.0min;By sample and standard substance Jing after head space process, by gas phase color Spectrum-mass spectrometric hyphenated technique is measured to acetone, isopropanol and methyl acetate;
(4) in sample various volatile ingredient measurement results calculating:According to the measurement result of standard working solution, with acetone, The peak area of isopropanol and methyl acetate distinguishes drawing curve to mass concentration, obtains standard working curve, then by sample Middle detection acetone, the peak area of isopropanol and methyl acetate substitute into standard working curve respectively, obtain acetone in sample, isopropanol and The content of methyl acetate.
2. the detection method that volatile ingredient is remained in hot-melt adhesive for cigarette according to claim 1, it is characterised in that:It is described In step (3), the condition of gas chromatogram is:Innowax fused quartz capillary chromatography posts (30m × 0.25mm × 0.25 μm);Enter Sample mouth temperature:250℃;Temperature programming:50 DEG C of initial temperature, keeps 2min, rises to 200 DEG C with 4 DEG C/min, keeps 10min;Point Stream sample introduction, split ratio 10:1;Carrier gas:Helium (purity is 99.999%);Constant current mode, flow velocity are 2.0mL/min;Sample size:1 μL。
3. the detection method that volatile ingredient is remained in hot-melt adhesive for cigarette according to claim 1 and 2, it is characterised in that: In the step (3), mass spectrographic condition is:EI ionizes pattern, ionization energy 70eV;Ion source temperature:230℃;Transmission line temperature: 250℃;150 DEG C of level Four bar temperature;Scanning of the mass spectrum mode:Full scan (SCAN), 30~350amu of sweep limitss.
4. the detection method that volatile ingredient is remained in hot-melt adhesive for cigarette according to claim 1, it is characterised in that:It is described In step (1) hybrid standard working solution, the mass concentration of acetone, isopropanol and methyl acetate is:1mg/L、2mg/L、4mg/ L、8mg/L、16mg/L。
CN201610935669.9A 2016-11-01 2016-11-01 Method for detecting volatiles residue in hot-melt adhesive for cigarettes Pending CN106526006A (en)

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Citations (8)

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Publication number Priority date Publication date Assignee Title
CN102103128A (en) * 2011-03-24 2011-06-22 中国烟草总公司郑州烟草研究院 Method for determining contents of formaldehyde, acetaldehyde and acetone in water-borne adhesives for cigarettes
CN102680624B (en) * 2012-05-07 2014-03-19 广东中烟工业有限责任公司 Method for detecting methyl acetate in adhesive for smoke
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CN102879511B (en) * 2012-09-27 2014-10-15 甘肃烟草工业有限责任公司 Method for determining volatile organic compounds in polyvinyl acetate type water-based adhesive
CN104198602A (en) * 2014-09-01 2014-12-10 云南中烟工业有限责任公司 Method for detecting vinyl acetate in hot melt adhesive
CN104330494A (en) * 2014-11-04 2015-02-04 广西中烟工业有限责任公司 Method for detecting halogenated hydrocarbon content in hot melt adhesive
US20150141319A1 (en) * 2005-12-07 2015-05-21 The Procter & Gamble Company Polymeric compositions for sustained release of volatile materials
CN106053620A (en) * 2016-05-11 2016-10-26 国家烟草质量监督检验中心 An HS-GC/MS based method for analyzing contents of volatile organic compounds in a water-based adhesive used for cigarettes

Patent Citations (8)

* Cited by examiner, † Cited by third party
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US20150141319A1 (en) * 2005-12-07 2015-05-21 The Procter & Gamble Company Polymeric compositions for sustained release of volatile materials
CN102103128A (en) * 2011-03-24 2011-06-22 中国烟草总公司郑州烟草研究院 Method for determining contents of formaldehyde, acetaldehyde and acetone in water-borne adhesives for cigarettes
CN102680624B (en) * 2012-05-07 2014-03-19 广东中烟工业有限责任公司 Method for detecting methyl acetate in adhesive for smoke
CN102680596B (en) * 2012-05-07 2014-03-19 广东中烟工业有限责任公司 Method for detecting organic volatile matters in adhesive for cigarettes
CN102879511B (en) * 2012-09-27 2014-10-15 甘肃烟草工业有限责任公司 Method for determining volatile organic compounds in polyvinyl acetate type water-based adhesive
CN104198602A (en) * 2014-09-01 2014-12-10 云南中烟工业有限责任公司 Method for detecting vinyl acetate in hot melt adhesive
CN104330494A (en) * 2014-11-04 2015-02-04 广西中烟工业有限责任公司 Method for detecting halogenated hydrocarbon content in hot melt adhesive
CN106053620A (en) * 2016-05-11 2016-10-26 国家烟草质量监督检验中心 An HS-GC/MS based method for analyzing contents of volatile organic compounds in a water-based adhesive used for cigarettes

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