CN109307719A - The measuring method of residual monomer and other organic principles in a kind of polychloroprene latex - Google Patents
The measuring method of residual monomer and other organic principles in a kind of polychloroprene latex Download PDFInfo
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- CN109307719A CN109307719A CN201710632146.1A CN201710632146A CN109307719A CN 109307719 A CN109307719 A CN 109307719A CN 201710632146 A CN201710632146 A CN 201710632146A CN 109307719 A CN109307719 A CN 109307719A
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- toluene
- styrene
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- 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
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- 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
- G01N30/16—Injection
Abstract
The present invention relates to the measuring methods of residual monomer and other organic principles in a kind of polychloroprene latex, using internal mark method determination, internal standard compound is methylisobutylketone, solvent is dioxane, main includes following two step: 1) the correction factor measurement of the styrene and toluene that evaporate in polychloroprene latex, 2) assay of the styrene and toluene evaporated in polychloroprene latex.Measuring method of the invention is reproducible, and accuracy is high.
Description
Technical field
The present invention relates to a kind of analysis methods of volatile component in raw material of industry.More particularly to using capillary column head space
The survey of volatile Determination of Styrene and volatile organic principle toluene in gas chromatograph quantitative analysis polychloroprene latex
Determine method.
Background technique
Synthetic rubber latex is the high molecular lotion of a kind of synthetic rubber, and type has carboxylic styrene butadiene latex, NBR latex
With polychloroprene latex etc., it can come directly as product using therefore being a kind of important high molecular material, in synthetic rubber work
It occupies an important position in industry.Synthetic rubber latex is widely used, is mainly used for manufacture foam rubber products, dipping system
In addition product are also largely used to carpet industry, paper industry, fiber treatment, construction material, coating, pigment, adhesive etc..Synthesis
The application field of rubber latex is also constantly expanding, and is expected to develop into an independent industrial department.
Unconverted monomer would generally be remained in synthetic rubber latex, they are mainly some alkenes compounds, and such as third
Alkene nitrile, styrene etc.；Meanwhile some organic principles can be also volatilized in synthetic rubber latex, such as toluene, ethylbenzene.Synthesize rubber
The problem of environmental pollution that residual monomer and other organic principles in glue latex attract also results in the extensive concern of society: such as third
Alkene nitrile, styrene, toluene, ethylbenzene etc. have more virulent property.Therefore, in view of the residual monomer in synthetic rubber latex and other have
The harm that machine ingredient may cause, it is necessary to establish the detection side of residual monomer and other organic principles in synthetic rubber latex
Method.
Currently, documents and materials report related synthetic rubber latex in residual monomer and other organic principles detection method
It is gas chromatography, there are two types of input modes, are as follows: direct-injection technique and headspace injection method.
Petrochemical industry standard SH/T 1760-2007 " residual monomer and other organic principles in synthetic rubber latex
Measure capillary column gas chromatography direct liquid introduction method ".The standard is using gas-chromatography direct-injection technique to synthetic rubber glue
Residual monomer and other organic principles are determined in cream." GC-MS method measures ABS, residual styrene and acrylonitrile in SAN
Monomer ", Shao Qiurong, " chemical analysis metering ", and the 1st phase of volume 24, page 80~82, in January, 2015.The document uses gas phase color
Spectrum-mass spectrum direct-injection technique is determined 2 kinds of residual monomer acrylonitrile and styrene in ABS, SAN plastics." acrylic acid and
The gas chromatography of residual monomer measures research in its esters polymer ", Liao Liewen, " Speciality Petrochemicals ", and the 1st phase, 2001
July in year.The document surveys the residual monomer in acrylic polymer using gas-chromatography direct-injection technique
It is fixed." Determination of Remaining Monomer in 791 Resin Powder by Gas Chromatography ", Chen Ping Zhang, " Shenyang chemical industry ", and the 6th phase, the 41st~43
Page, 1997.The document is determined the residual monomer in 791 resin-oatmeals using gas-chromatography direct-injection technique.
CN201010614229.6 discloses a kind of gas-chromatography direct-injection technique test acrylate pressure-sensitive adhesive residual monomer content
Method." the survey of residual monomer and solvent in food packaging acrylonitritrile-styrene resin and rubber modified resin and molded product
It is fixed ", Sun Duozhi, " physical and chemical inspection ", volume 47, page 1443~1445,2011 years.The document uses gas-chromatography direct injected
Method is determined to the residual monomer in acrylonitritrile-styrene resin and rubber modified resin and molded product." gas phase color
Spectrometry measures residual monomer in ABS resin ", warm hypo, " Chemical Engineer ", and the 3rd phase of volume 96, page 23~24,2003 years 6
Month.The document is determined the residual monomer in ABS resin using gas-chromatography direct-injection technique." acrylic nitrile-butadiene two
The dissolution precipitating of residual monomer-gas chromatography measurement in alkene-styrene (ABS) plastics ", Yuan Lifeng, " analysis test journal ",
The 10th phase of volume 27, page 1095~1098, in October, 2008.The document is using gas-chromatography direct-injection technique to acrylonitrile-
9 kinds of poisonous and harmful residual monomers are determined in butadiene-styrene (ABS) plastics." residual monomer in polymer emulsion
Gas Chromatographic Determination ", Yu Yanjun, " chromatography ", and the 1st phase of volume 7, page 56~57,1989 years.The document is straight using gas-chromatography
Sampling system is connect to be determined the residual monomer in polymer emulsion.
Above-mentioned nine documents are all made of gas-chromatography direct-injection technique, and sample is directly injected into gas phase color with sample introduction needle
In spectrometer, the blocking of sample introduction needle is not only resulted in this way, gas chromatograph system can also be formed and be polluted, influence subsequent sample point
Analyse the accuracy of result.
International standard ISO 13741-2 " plastics/rubber-polymeric dispersions and rubber latex (natural and synthesis)-
Residual monomer and other organic principle headspace injection methods are measured with Capillary Column GC ", which uses gas-chromatography
Headspace injection method is to residual monomer in plastics/rubber-polymeric dispersions and rubber latex (natural and synthesis) and other
Organic principle is determined, and internal standard quanitation is used in continuous mode, and the solvent used is dimethylformamide or diformazan
Yl acetamide, the internal standard compound used are dioxane or methylisobutylketone, specific testing procedure are as follows: (1) by internal standard compound and list
A Component Standard substance or the standard substance of multiple components are made into mixed solution；(2) by 1cm3Water and 2cm3Mixed solution it is mixed
It closes, takes the top tank air injecting chromatograph of the mixed liquor of certain volume (50 μ L of <) (it is recommended that the sample of 3 to 4 various concentrations of measurement
Product)；(3) peak area for measuring each determinand, calculates correction factor；(4) sample for weighing 0.5g, is added to headspace sampling
In the ml headspace bottle of device, 1cm is then added3Water and 2cm3Inner mark solution, add the ml headspace bottle of head-space sampler is close after dottle pin
Envelope；Herein, the water being added in rubber latex sample is in " 6682-2008 water for analytical laboratory use-Specification and test methods of GB/T "
Defined level-one water；(5) 30min~4h will be stirred with magnetic stirrer；(6) at 90 DEG C, sample solution is heated into 1h, makes sample
After product vapor liquid equilibrium, the ml headspace bottle of head-space sampler gas at the middle and upper levels is detected；(7) peak area and determinand of internal standard compound are measured
Peak area；(8) content of volatile residual monomer and other organic principles in latex is finally obtained by calculating.
" Gas Chromatographic Method of residual monomer and volatile component in styrene series resin ", Wu Keqin, " high bridge
Petrochemical industry ", the 1st phase of volume 17, page 16~18,2 months 2002 years.The document using GC headspace injection method to PS, AS and
Residual monomer and volatile component are determined in ABS plastic resin.When measurement, using inner mark method ration, dimethyl methyl is used
Solvent of the amide as inner mark solution and Standard Stock solutions, is determined the residual monomer in styrene series resin.
" Determination of Styrene in Polystyrene by Gas Chromatography ", Zhu Shenghui, " Modern Scientific Instruments ", page 83~85,
2 months 2008.The document is determined Residuce of Styrene in polystyrene using GC headspace injection method.It surveys
Periodically, using inner mark method ration, use dimethylformamide as the solvent of inner mark solution and Standard Stock solutions, to polystyrene
In Determination of Styrene be determined." the residual monomer measurement in vinylacetate and crotonic acid copolymers ", Chen Jian
Sea, " chemistry world ", the 1st phase, page 48~49,1993 years.The document uses GC headspace injection method Dichlorodiphenyl Acetate ethylene
Residual monomer in ester and crotonic acid copolymers is determined.When measurement, using inner mark method ration, made with dimethyl acetamide
For the solvent of inner mark solution and Standard Stock solutions, the residual monomer in Dichlorodiphenyl Acetate vinyl acetate and crotonic acid copolymers is surveyed
It is fixed." the GC-MS method of the Determination of Styrene in kayexalate resin measures ", Chen Fang, " Chinese Medicine industry is miscellaneous
Will ", the 1st phase of volume 41, page 32~34, in January, 2010.The document is using GC headspace injection method to polystyrene sulphur
Determination of Styrene in sour sodium resin is determined.When measurement, using inner mark method ration,
Use methanol as the solvent of inner mark solution and Standard Stock solutions, to the residual list in kayexalate resin
Body styrene is determined." residual monomer content in Headspace Gas Chromatography styrene-acrylic emulsion ", Lu Ting, " China applies
Material ", the 7th phase of volume 29, page 66~70, in July, 2014.The document is using GC headspace injection method in styrene-acrylic emulsion
Residual monomer be determined.When measurement, using inner mark method ration, use water as the solvent of inner mark solution, acetone is as mark
Quasi- stock solution solvent, is determined the residual monomer in styrene-acrylic emulsion.
Above-mentioned six documents are all made of GC headspace injection method and are measured to the residual monomer in sample.It adopts
When with Head space sample introduction, needs first to heat sample, then take the gas phase injecting chromatograph on sample upper layer to be analyzed, thus keep away
Blocking of the sample sample introduction needle and the pollution caused by instrument when direct injected are exempted from.Above-mentioned six documents measurement when,
Internal standard method is all made of to quantify.Preceding four documents using dimethylformamide or dimethyl acetamide as inner mark solution with
The solvent of Standard Stock solutions, then two documents have then used methanol or acetone as solvent to prepare standard storage respectively
Standby solution.It is using the major defect that dimethylformamide or dimethyl acetamide make solvent, in the test process of sample,
Dimethylformamide can in disturbed specimen main component toluene appearance, and dimethyl acetamide then can be main group in disturbed specimen
The appearance of point ethylbenzene, this will directly influence the precision of toluene or the quantitative accuracy and this method of ethylbenzene；Use methanol
When making solvent with acetone, because their boiling point is relatively low, qualitative, quantitative point of the more early component of appearance time in sample will affect
Analysis.
Summary of the invention
The object of the present invention is to provide the measuring methods of residual monomer and other organic principles in a kind of polychloroprene latex, specifically
It is the measuring method of volatile Determination of Styrene and volatile organic principle toluene in polychloroprene latex.The present invention is especially
Volatile Determination of Styrene and volatile organic principle first suitable for using inner mark method ration measurement polychloroprene latex
The method of benzene.
The measuring method of residual monomer and other organic principles in a kind of polychloroprene latex, using internal mark method determination, internal standard compound
For methylisobutylketone, solvent is dioxane, mainly includes following two step: the 1) styrene evaporated in polychloroprene latex
Measured with the correction factor of toluene, 2) assay of styrene and toluene that evaporates in polychloroprene latex.
Step 1) the correction factor measurement needs to prepare inner mark solution and Standard Stock solutions, wraps in Standard Stock solutions
Two kinds of standard substance styrene and toluene are included, the internal standard compound of inner mark solution is methylisobutylketone, and the solvent of inner mark solution is dioxy
Own ring；According to the peak area of two kinds of standard substances, the correction factor of two kinds of standard substances is calculated by formula (1).
In formula:
RfThe correction factor of-standard substance；AsThe peak area of-internal standard compound；mv oThe quality of-standard substance, unit are gram
(g)；AvThe peak area of-standard substance；ms oThe quality of-internal standard compound, unit are gram (g).
The assay of two kinds of determinand styrene of the step 2) and toluene is mainly to be measured according to internal standard compound and two kinds
The peak area of object styrene and toluene；By the content for calculating each determinand in polychloroprene latex sample to be measured according to formula (2).
In formula: AvThe peak area of-determinand；msThe quality of-step (2) internal standard compound, unit are milligram (mg)；Rf- by
The correction factor that formula (1) obtains；AsThe peak area of-internal standard compound；mdThe quality of-polychloroprene latex sample to be measured, unit are kilogram
(kg)。
Volatile Determination of Styrene and volatile organic principle toluene in polychloroprene latex of the present invention
The correction factor of measuring method, the styrene predominantly evaporated in polychloroprene latex and toluene measures, neoprene milk sample to be measured
Two steps of assay of the styrene and toluene that are evaporated in product.Detailed process is as follows:
(1) correction factor of the styrene and toluene that evaporate in polychloroprene latex measures
Before measuring correction factor, need to prepare inner mark solution and Standard Stock solutions, the preparation of inner mark solution are as follows: match first
Concentration range processed is 300 μ g/cm3~600 μ g/cm3Inner mark solution, internal standard compound is methylisobutylketone, and solvent is dioxane；
Standard Stock solutions include two kinds of standard substance styrene and toluene: the volume of two kinds of standard substance styrene and toluene and solvent
Than for 1:30~1:60, solvent is dioxane.
The specific continuous mode of correction factor are as follows: store up water, inner mark solution and standard by the proportion of 1:2:15~1:4:45
Standby solution, which is placed in the ml headspace bottle of head-space sampler, to be mixed, and the ml headspace bottle of head-space sampler is sealed, by the upper layer gas of mixed solution
Body injecting chromatograph；According to the peak area of standard substance, the correction factor of standard substance is calculated by formula (1):
In formula:
RfThe correction factor of-standard substance；
AsThe peak area of-internal standard compound；
mv oThe quality of the ml headspace bottle Plays substance of-step (1) head-space sampler, unit are gram (g)；
AvThe peak area of-standard substance；
ms oThe quality of internal standard compound in the ml headspace bottle of-step (1) head-space sampler, unit are gram (g).
(2) assay of the styrene and toluene evaporated in polychloroprene latex sample to be measured
The polychloroprene latex sample to be measured for weighing 0.3g~1.0g, is added in the ml headspace bottle of head-space sampler；Then it is added
After the water of 0.8mL~1.1mL and the inner mark solution of 1.8mL~2.2mL, the ml headspace bottle of head-space sampler is sealed；It is stirred with electromagnetism
Mix device stirring 0.5h~4.0h；At 70 DEG C~90 DEG C, 0.5h~2.0h is heated, to the sample in the ml headspace bottle of head-space sampler
After vapor liquid equilibrium, by the ml headspace bottle of head-space sampler gas injecting chromatograph at the middle and upper levels, obtain internal standard compound and determinand styrene,
The peak area of toluene；The content of styrene and toluene in polychloroprene latex sample to be measured is calculated according to formula (2):
In formula:
Av--- the peak area of determinand；
ms--- the quality of internal standard compound in the ml headspace bottle of step (2) head-space sampler, unit are milligram (mg)；
Rf--- the correction factor obtained by formula (1)；
As--- the peak area of internal standard compound；
md--- the quality of polychloroprene latex sample to be measured in the ml headspace bottle of step (2) head-space sampler, unit are kilogram
(kg)。
Synthetic rubber latex of the present invention is polychloroprene latex.
Quantitative approach of the present invention is internal standard quanitation.
Volatile residual monomer is styrene in polychloroprene latex of the present invention.
Volatile organic principle is toluene in polychloroprene latex of the present invention.
Internal standard compound described in step (1) of the present invention is methylisobutylketone, and solvent is dioxane, the purity of two kinds of reagents
It is that analysis is pure.
Water described in step (1) of the present invention is level-one water specified in GB/T 6682-2008.
Standard substance described in step (1) of the present invention is styrene and toluene.
Chromatographic condition of the present invention includes two parts of gas chromatograph and head-space sampler, wherein gas chromatograph
Condition are as follows: injector temperature be 150 DEG C~250 DEG C, split ratio 10:1, column head pressure 12.0psi, starting column temperature be 30
DEG C~50 DEG C, preferably 30 DEG C~40 DEG C, retains 10min, 170 DEG C, preferably 3 are risen to 2 DEG C/min~6 DEG C/min heating rate
DEG C/min~5 DEG C/min, do not retain, then rises to 250 DEG C again with 8 DEG C/min~11 DEG C/min heating rate, preferably 9 DEG C/
Min~10 DEG C/min, do not retain, and detector temperature is 250 DEG C~300 DEG C；The condition of head-space sampler are as follows: sample injector furnace temperature is
80 DEG C~95 DEG C, preferably 90 DEG C~95 DEG C, sample injector furnace temperature soaking time be 40min~70min, preferably 55min~65min,
Sampling probe temperature be 100 DEG C, transmission line temperature be 110 DEG C, nebulizer gas pressure 20.0psi, sample injection time be 0.01min~
0.04min, preferably 0.02min~0.03min, pulling out the needle time is 0.2min, and pressurize 3.0min.
Gas chromatograph of the present invention need to be furnished with flame ionization ditector (FID).
The present invention for gas chromatograph and head-space sampler model and be not limited, the gas suitable for various models
Chromatography and head-space sampler.
The present invention using GC headspace injection method to volatile Determination of Styrene in polychloroprene latex sample and
Volatile organic principle toluene is measured, and avoids blocking of the polychloroprene latex sample to sample introduction needle when direct injected in this way
It is polluted with caused by instrument, eliminates the qualitative, quantitative effect caused by subsequent sample.
The present invention when using inner mark method ration, compared with the existing technology in it is in correction factor determination step that internal standard is molten
Liquid and Standard Stock solutions mixed preparing, the present invention is in correction factor determination step, by inner mark solution and Standard Stock solutions
It is separately formulated, in this way in polychloroprene latex sample to be measured in the styrene evaporated and the determination step of toluene level, with regard to nothing
It needs to prepare inner mark solution again again；The time is both saved in this way, simplifies operating process, and reduces the use of reagent, is saved
Cost, while also reducing the pollution to environment.
Inner mark solution of the invention is the mixed solution of methylisobutylketone and dioxane, compared with the existing technology middle internal standard
Solution is methyl for the mixed solution of methylisobutylketone (or dioxane) and dimethylformamide (or dimethyl acetamide)
The inner mark solution that isobutyl ketone is combined with dioxane has the characteristics that toxicity is low, what the health and environment to user generated
Pollution effect is smaller, more environmentally friendly.
Standard Stock solutions of the invention are the mixed solution of dioxane and two kinds of standard substance styrene and toluene, phase
For using dimethylformamide (or dimethyl acetamide) to prepare standard inventory as solvent and standard substance in the prior art
For solution, the Standard Stock solutions that dioxane is combined with two kinds of reference substances not only have the characteristics that toxicity is low, but also overcome
When dimethylformamide makees solvent in the prior art, solvent peak hangover is serious, disturbs the appearance of toluene in standard substance, keeps away
When having exempted to make solvent using dimethylformamide, since the hangover of solvent peak causes solvent and rubber latex sample component separating degree to drop
Disadvantage low, sensitivity is weak；Ensure using prepare Standard Stock solutions measurement toluene correction factor accuracy and can
By property；Meanwhile improving the precision of our standard measure.
Using GC headspace injection method to the two kinds of determinand styrene and toluene evaporated in polychloroprene latex
When content is measured, choose dioxane make solvent prepare inner mark solution be added in polychloroprene latex sample to be measured, can make to
The head space peak area for surveying the determinand toluene evaporated in polychloroprene latex sample is respectively increased 6%~8% compared with the prior art, this
A result illustrates the head space detection sensitivity that toluene can be improved as solvent using dioxane.
The headspace gas chromatography instrument that measuring method of the invention uses is easy to operate, reproducible, and it is to be directed to that accuracy is high
Complicated component and the optimal path of instrument sample easy to pollute analysis.
Detailed description of the invention
Fig. 1 is that the Chromatographic Comparison of dimethylformamide and polychloroprene latex sample schemes, and in figure, 1 is dimethylformamide；2 are
Toluene.
Fig. 2 is that the Chromatographic Comparison of dioxane and polychloroprene latex sample schemes, and in figure, 3 be dioxane；4 be toluene.
Specific embodiment
Illustrate the present invention by the following examples, however, the present invention is not limited to these examples.
Synthetic rubber latex used in the present invention is polychloroprene latex, dimethylformamide used, methylisobutylketone and two
Pentamethylene oxide is commercially available analytical reagents, instrument used in the present invention are as follows: the Shanghai Pu Mei Ying instrument and meter Manufacturing Co., Ltd
The H97-A type magnetic stirrer of production, the 7890A gas chromatograph of Agilent company of U.S. production and the production of PE company of the U.S.
Tubomatrix HS40-trap head-space sampler.
Embodiment 1
(1) correction factor of the styrene and toluene that evaporate in polychloroprene latex measures
The internal standard compound methylisobutylketone for weighing 17.0mg (being accurate to 0.1mg) is added in the volumetric flask of 50mL, uses dioxy
Own ring solvent is diluted to graduation mark, and sealing is used as inner mark solution after shaking up；The internal standard compound methylisobutylketone of about 4.0mL is taken to be added to
In the volumetric flask of 10mL, add three kinds of styrene, toluene and ethylbenzene standard substances respectively about 220 μ L (every kind of about 0.18g, accurately
To 0.1mg), it is diluted to graduation mark with dioxane solvent, sealing is used as Standard Stock solutions after shaking up.
The Standard Stock solutions of 0.8mL water, 1.5mL inner mark solution and 25 μ L are placed in the ml headspace bottle of head-space sampler and are mixed
It closes, the ml headspace bottle of head-space sampler is sealed, by the top tank air injecting chromatograph of mixed solution；In the condition of gas chromatograph
Are as follows: injector temperature is 180 DEG C, split ratio 10:1, column head pressure 12.0psi, and starting column temperature is 40 DEG C, retains 10min,
170 DEG C are risen to the heating rate of 2 DEG C/min, is not retained, then 250 DEG C is risen to again with the heating rate of 8 DEG C/min, does not protect
It stays, detector temperature is 250 DEG C；The condition of head-space sampler are as follows: sample injector furnace temperature is 85 DEG C, and sample injector furnace temperature soaking time is
65min, sampling probe temperature are 100 DEG C, and transmission line temperature is 110 DEG C, nebulizer gas pressure 20.0psi, and sample injection time is
0.04min, pulling out the needle time is 0.2min, is measured under the 3.0min that pressurizes, obtains the peak face of internal standard compound and two kinds of standard substances
Product, calculates correction factor by formula (1):
In formula:
RfThe correction factor of-standard substance；
AsThe peak area of-internal standard compound；
mv oThe quality of the ml headspace bottle Plays substance of-step (1) head-space sampler, unit are gram (g)；
AvThe peak area of-standard substance；
ms oThe quality of internal standard compound in the ml headspace bottle of-step (1) head-space sampler, unit are gram (g).
Calculated correction factor is shown in Table 1.
The correction factor of the styrene and toluene that are evaporated in 1 polychloroprene latex of table
| Determinand | Correction factor |
| Toluene | 0.3 |
| Styrene | 1.1 |
(2) assay of the styrene and toluene evaporated in polychloroprene latex sample to be measured
The polychloroprene latex sample for weighing 0.9g, is added in the ml headspace bottle of head-space sampler；Then be added 0.9mL water and
After the inner mark solution of 2.0mL, the ml headspace bottle of head-space sampler is sealed；With magnetic stirrer 2.0h；At 85 DEG C, heating
1.0h, after sample to be tested vapor liquid equilibrium, by the ml headspace bottle of head-space sampler gas injecting chromatograph at the middle and upper levels, in above-mentioned gas phase color
Under conditions of spectrometer, the peak area of internal standard compound and two kinds of determinand styrene and toluene is obtained；Chlorine to be measured is calculated according to formula (2)
The content of each determinand in fourth rubber latex sample:
In formula:
Av--- the peak area of determinand；
ms--- the quality of internal standard compound in the ml headspace bottle of step (2) head-space sampler, unit are milligram (mg)；
Rf--- the correction factor obtained by formula (1)；
As--- the peak area of internal standard compound；
md--- the quality of polychloroprene latex sample to be measured in the ml headspace bottle of step (2) head-space sampler, unit are kilogram
(kg)。
The content for calculating the two kinds of determinand styrene and toluene that evaporate in polychloroprene latex sample to be measured is shown in Table 2.
The content of two kinds of determinand styrene and toluene being evaporated in the polychloroprene latex sample to be measured of table 2
When the determinand evaporated in measuring polychloroprene latex sample, the prior art makees solvent using dimethylformamide
It prepares inner mark solution and Standard Stock solutions, the chromatogram made is shown in Fig. 1.In Fig. 1, the expression of chromatographic peak 1 is dimethyl
Formamide, peak shape is poor, hangover is serious, larger to toluene peak (chromatographic peak 2) interference close with its retention time.The present invention
Method measure polychloroprene latex sample in evaporate determinand when, using dioxane as solvent prepare inner mark solution with
Standard Stock solutions, the chromatogram made are shown in Fig. 2.In Fig. 2, the expression of chromatographic peak 3 is dioxane, and chromatographic peak 4 indicates
It is toluene.From figure 2 it can be seen that the chromatographic peak peak shape of dioxane is symmetrical, without trailing phenomenon, and dioxane
Retention time differs larger with the retention time of toluene, avoids the dimethylformamide influence quantitative to toluene.
Embodiment 2
(1) correction factor of the styrene and toluene that evaporate in polychloroprene latex measures
The internal standard compound methylisobutylketone for weighing 23.0mg (being accurate to 0.1mg) is added in the volumetric flask of 50mL, uses dioxy
Own ring solvent is diluted to graduation mark, and sealing is used as inner mark solution after shaking up；The internal standard compound methylisobutylketone of about 4.5mL is taken to be added to
In the volumetric flask of 10mL, adding two kinds of standard substances of styrene and toluene, respectively (every kind of about 0.18g, is accurate to about 200 μ L
After 0.1mg), it is diluted to graduation mark with dioxane solvent, sealing is used as Standard Stock solutions after shaking up.
The Standard Stock solutions of 0.6mL water, 1.0mL inner mark solution and 28 μ L are placed in the ml headspace bottle of head-space sampler and are mixed
It closes, the ml headspace bottle of head-space sampler is sealed, by the top tank air injecting chromatograph of mixed solution；In the condition of gas chromatograph
Are as follows: injector temperature is 230 DEG C, split ratio 10:1, column head pressure 12.0psi, and starting column temperature is 35 DEG C, retains 10min,
170 DEG C are risen to the heating rate of 3 DEG C/min, is not retained, then 250 DEG C is risen to again with the heating rate of 10 DEG C/min, does not protect
It stays, detector temperature is 270 DEG C；The condition of head-space sampler are as follows: sample injector furnace temperature is 80 DEG C, and sample injector furnace temperature soaking time is
60min, sampling probe temperature are 100 DEG C, and transmission line temperature is 110 DEG C, nebulizer gas pressure 20.0psi, and sample injection time is
0.01min, pulling out the needle time is 0.2min, is measured under the 3.0min that pressurizes, obtains the peak face of internal standard compound and two kinds of standard substances
Product, calculates correction factor by formula (1):
In formula:
RfThe correction factor of-standard substance；
AsThe peak area of-internal standard compound；
mv oThe quality of the ml headspace bottle Plays substance of-step (1) head-space sampler, unit are gram (g)；
AvThe peak area of-standard substance；
ms oThe quality of internal standard compound in the ml headspace bottle of-step (1) head-space sampler, unit are gram (g).
Calculated correction factor is shown in Table 3.
The correction factor of the styrene and toluene that are evaporated in 3 polychloroprene latex of table
| Determinand | Correction factor |
| Toluene | 0.2 |
| Styrene | 1.1 |
(2) assay of the styrene and toluene evaporated in polychloroprene latex sample to be measured
The polychloroprene latex sample for weighing 0.7g, is added in the ml headspace bottle of head-space sampler；Then be added 1.1mL water and
After the inner mark solution of 1.9mL, the ml headspace bottle of head-space sampler is sealed；With magnetic stirrer 3.0h；At 75 DEG C, heating
1.5h, after sample to be tested vapor liquid equilibrium, by the ml headspace bottle of head-space sampler gas injecting chromatograph at the middle and upper levels, in above-mentioned gas phase color
Under conditions of spectrometer, the peak area of internal standard compound and two kinds of determinand styrene and toluene is obtained；Chlorine to be measured is calculated according to formula (2)
The content of each determinand in fourth rubber latex sample:
In formula:
Av--- the peak area of determinand；
ms--- the quality of internal standard compound in the ml headspace bottle of step (2) head-space sampler, unit are milligram (mg)；
Rf--- the correction factor obtained by formula (1)；
As--- the peak area of internal standard compound；
md--- the quality of polychloroprene latex sample to be measured in the ml headspace bottle of step (2) head-space sampler, unit are kilogram
(kg)。
The content for calculating the two kinds of determinand styrene and toluene that evaporate in polychloroprene latex sample to be measured is shown in Table 4.
The content of two kinds of determinand styrene and toluene being evaporated in the polychloroprene latex sample to be measured of table 4
When the determinand evaporated in measuring polychloroprene latex sample, the prior art makees solvent using dimethylformamide
Inner mark solution and Standard Stock solutions, the chromatogram made and the method for the present invention is prepared to volatilize in measurement polychloroprene latex sample
When determinand out, inner mark solution and Standard Stock solutions, the chromatogram made are prepared as solvent using dioxane
It is similar to Example 1.When overcoming that dimethylformamide makees solvent in the prior art, solvent peak hangover is serious, disturbs standard
When the appearance or dimethyl acetamide of toluene make solvent in substance, solvent peak hangover, ethylbenzene in severe jamming standard substance
Appearance avoids when making solvent using dimethylformamide or dimethyl acetamide, due to the hangover of solvent peak cause solvent with
The disadvantage that rubber latex sample component separating degree reduces, sensitivity is weak；Ensure the toluene using the Standard Stock solutions measurement prepared
With the accuracy and reliability of ethylbenzene correction factor.
Embodiment 3
(1) correction factor of the styrene and toluene that evaporate in polychloroprene latex measures
The internal standard compound methylisobutylketone for weighing 20.0mg (being accurate to 0.1mg) is added in the volumetric flask of 50mL, uses dioxy
Own ring solvent is diluted to graduation mark, and sealing is used as inner mark solution after shaking up；The internal standard compound methylisobutylketone of about 3.5mL is taken to be added to
In the volumetric flask of 10mL, adding two kinds of standard substances of styrene and toluene, respectively (every kind of about 0.18g, is accurate to about 210 μ L
After 0.1mg), it is diluted to graduation mark with dioxane solvent, sealing is used as Standard Stock solutions after shaking up.
The Standard Stock solutions of 0.9mL water, 1.5mL inner mark solution and 28 μ L are placed in the ml headspace bottle of head-space sampler and are mixed
It closes, the ml headspace bottle of head-space sampler is sealed, by the top tank air injecting chromatograph of mixed solution；In the condition of gas chromatograph
Are as follows: injector temperature is 200 DEG C, split ratio 10:1, column head pressure 12.0psi, and starting column temperature is 40 DEG C, retains 10min,
170 DEG C are risen to the heating rate of 3 DEG C/min, is not retained, then 250 DEG C is risen to again with the heating rate of 8 DEG C/min, does not protect
It stays, detector temperature is 270 DEG C；The condition of head-space sampler are as follows: sample injector furnace temperature is 90 DEG C, and sample injector furnace temperature soaking time is
55min, sampling probe temperature are 100 DEG C, and transmission line temperature is 110 DEG C, nebulizer gas pressure 20.0psi, and sample injection time is
0.02min, pulling out the needle time is 0.2min, is measured under the 3.0min that pressurizes, obtains the peak face of internal standard compound and two kinds of standard substances
Product, calculates correction factor by formula (1):
In formula:
RfThe correction factor of-standard substance；
AsThe peak area of-internal standard compound；
mv oThe quality of the ml headspace bottle Plays substance of-step (1) head-space sampler, unit are gram (g)；
AvThe peak area of-standard substance；
ms oThe quality of internal standard compound in the ml headspace bottle of-step (1) head-space sampler, unit are gram (g).
Calculated correction factor is shown in Table 5.
The correction factor of the styrene and toluene that are evaporated in 5 polychloroprene latex of table
| Determinand | Correction factor |
| Toluene | 0.2 |
| Styrene | 1.0 |
(2) assay of the styrene and toluene evaporated in polychloroprene latex sample to be measured
The polychloroprene latex sample for weighing 0.6g, is added in the ml headspace bottle of head-space sampler；Then be added 0.8mL water and
After the inner mark solution of 2.0mL, the ml headspace bottle of head-space sampler is sealed；With magnetic stirrer 1.5h；At 90 DEG C, heating
1.0h, after sample to be tested vapor liquid equilibrium, by the ml headspace bottle of head-space sampler gas injecting chromatograph at the middle and upper levels, in above-mentioned gas phase color
Under conditions of spectrometer, the peak area of internal standard compound and two kinds of determinand styrene and toluene is obtained；Chlorine to be measured is calculated according to formula (2)
The content of each determinand in fourth rubber latex sample:
In formula: Av--- the peak area of determinand；
ms--- the quality of internal standard compound in the ml headspace bottle of step (2) head-space sampler, unit are milligram (mg)；
Rf--- the correction factor obtained by formula (1)；
As--- the peak area of internal standard compound；
md--- the quality of polychloroprene latex sample to be measured in the ml headspace bottle of step (2) head-space sampler, unit are kilogram
(kg)。
The content for calculating the two kinds of determinand styrene and toluene that evaporate in polychloroprene latex sample to be measured is shown in Table 6.
The content of two kinds of determinand styrene and toluene being evaporated in the polychloroprene latex sample to be measured of table 6
When the determinand evaporated in measuring polychloroprene latex sample, the prior art makees solvent using dimethylformamide
Inner mark solution and Standard Stock solutions, the chromatogram made and the method for the present invention is prepared to volatilize in measurement polychloroprene latex sample
When determinand out, inner mark solution and Standard Stock solutions, the chromatogram made are prepared as solvent using dioxane
It is similar to Example 1.When overcoming that dimethylformamide makees solvent in the prior art, solvent peak hangover is serious, disturbs standard
When the appearance or dimethyl acetamide of toluene make solvent in substance, solvent peak hangover, ethylbenzene in severe jamming standard substance
Appearance avoids when making solvent using dimethylformamide or dimethyl acetamide, due to the hangover of solvent peak cause solvent with
The disadvantage that rubber latex sample component separating degree reduces, sensitivity is weak；Ensure the toluene using the Standard Stock solutions measurement prepared
With the accuracy and reliability of ethylbenzene correction factor.
Comparative example 1~2
According to method as defined in international standard ISO 13741-2, using dimethylformamide make solvent prepare internal standard compound with
The mixed solution of standard substance respectively surveys the toluene level evaporated in the polychloroprene latex of embodiment 1 and embodiment 2
Fixed, measurement the results are shown in Table 7.
From embodiment 1, embodiment 2 and comparative example 1~2 as can be seen that for polychloroprene latex, embodiment 1 measures toluene peak
The average value of area is 2529, and the relative standard deviation that embodiment 1 measures toluene is 1.37%, and embodiment 2 measures toluene peak face
Long-pending average value is 3240, and the relative standard deviation that embodiment 2 measures toluene is 3.21%, and comparative example 1 measures toluene peak area
Average value be 2452, comparative example 1 measure toluene relative standard deviation be 4.12%, comparative example 2 measures toluene peak area
Average value is 3035, and the relative standard deviation that comparative example 2 measures toluene is 4.99%.By being compared above as can be seen that this hair
When the determinand that bright method evaporates in measuring polychloroprene latex sample to be measured, internal standard is prepared as solvent using dioxane
Solution and Standard Stock solutions not only avoid the dimethylformamide chromatographic peak hangover influence quantitative to toluene, and it is good to have obtained
Repeatability, and the head space peak area of toluene can be made to improve 6%~8% compared with the prior art, i.e., the head space of toluene be detected into spirit
Sensitivity is improved.
In 7 comparative example 1-2 of table in polychloroprene latex sample to be measured toluene repeated experiment data
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (10)
1. the measuring method of residual monomer and other organic principles in a kind of polychloroprene latex, which is characterized in that surveyed using internal standard method
Fixed, internal standard compound is methylisobutylketone, and solvent is dioxane, including following two step: 1) evaporating in polychloroprene latex
The measurement of the correction factor of styrene and toluene, 2) assay of the styrene and toluene that evaporate in polychloroprene latex.
2. measuring method according to claim 1, which is characterized in that in step 1) the correction factor measurement needs to prepare
Mark solution and Standard Stock solutions, include two kinds of standard substance styrene and toluene in Standard Stock solutions, inner mark solution it is interior
Mark object is methylisobutylketone, and the solvent of inner mark solution is dioxane；According to the peak area of two kinds of standard substances, by formula (1)
The correction factor of two kinds of standard substances is calculated,
In formula, RfThe correction factor of-standard substance；AsThe peak area of-internal standard compound；mv oThe quality of-standard substance, unit are
Gram；AvThe peak area of-standard substance；ms oThe quality of-internal standard compound, unit are gram.
3. measuring method according to claim 1, which is characterized in that two kinds of determinand styrene of the step 2) and toluene
Assay be that neoprene to be measured is calculated by formula (2) according to the peak area of internal standard compound and two kinds of determinand styrene and toluene
The content of each determinand in rubber latex sample,
In formula, AvThe peak area of-determinand；msThe quality of-step (2) internal standard compound, unit is milligram；Rf- obtained by formula (1)
The correction factor arrived；AsThe peak area of-internal standard compound；mdThe quality of-polychloroprene latex sample to be measured, unit are kilogram.
4. measuring method according to claim 2, which is characterized in that the process for preparation of the inner mark solution are as follows: prepare dense
Degree range is 300 μ g/cm3~600 μ g/cm3Inner mark solution, internal standard compound is methylisobutylketone, and solvent is dioxane；Standard
Stock solution includes two kinds of standard substance styrene and toluene, and the volume ratio of two kinds of standard substance styrene and toluene and solvent is
1:30~1:60, solvent are dioxane.
5. measuring method according to claim 2, which is characterized in that the specific continuous mode of the correction factor are as follows: press
Water, inner mark solution are placed in the ml headspace bottle of head-space sampler with Standard Stock solutions and are mixed by the proportion of 1:2:15~1:4:45,
The ml headspace bottle for sealing head-space sampler, by the top tank air injecting chromatograph of mixed solution；According to the peak area of standard substance, by
Formula (1) calculates the correction factor of standard substance.
6. measuring method according to claim 3, which is characterized in that the content of described two determinand styrene and toluene
Continuous mode is as follows: weighing the polychloroprene latex sample to be measured of 0.3g~1.0g, is added in the ml headspace bottle of head-space sampler；Then
After the water of 0.8mL~1.1mL and the inner mark solution of 1.8mL~2.2mL is added, the ml headspace bottle of head-space sampler is sealed；Electricity consumption
Magnetic stirrer stirs 0.5h~4.0h；At 70 DEG C~90 DEG C, 0.5h~2.0h is heated, in the ml headspace bottle of head-space sampler
After sample vapor liquid equilibrium, by the ml headspace bottle of head-space sampler gas injecting chromatograph at the middle and upper levels, internal standard compound and determinand benzene are obtained
The peak area of ethylene, toluene；The content of styrene and toluene in polychloroprene latex sample to be measured is calculated according to formula (2).
7. measuring method according to claim 5 or 6, which is characterized in that the chromatographic condition are as follows: injector temperature
It is 150 DEG C~250 DEG C, split ratio 10:1, column head pressure 12psi, starting column temperature is 30 DEG C~50 DEG C, retain 10min, with
The heating rate of 2 DEG C/min~6 DEG C/min rises to 170 DEG C, does not retain, then again with 8 DEG C/min~11 DEG C/min heating speed
Rate rises to 250 DEG C, does not retain, and detector temperature is 250 DEG C~300 DEG C.
8. measuring method according to claim 7, which is characterized in that the chromatographic condition are as follows: injector temperature is
150 DEG C~250 DEG C, split ratio 10:1, column head pressure 12psi, starting column temperature is 30 DEG C~40 DEG C, retains 10min, with 3
DEG C/min~5 DEG C/min heating rate rises to 170 DEG C, do not retain, then again with 9 DEG C/min~10 DEG C/min heating rate
250 DEG C are risen to, is not retained, detector temperature is 250 DEG C~300 DEG C.
9. measuring method according to claim 5 or 6, which is characterized in that the condition of the head-space sampler are as follows: sample injector
Furnace temperature is 80 DEG C~95 DEG C, and sample injector furnace temperature soaking time is 40min~70min, and sampling probe temperature is 100 DEG C, transmission line temperature
Degree is 110 DEG C, nebulizer gas pressure 20psi, and sample injection time is 0.01min~0.04min, and pulling out the needle time is 0.2min, pressurization
3.0min。
10. measuring method according to claim 9, which is characterized in that the condition of the head-space sampler are as follows: sample injector furnace
Temperature is 90 DEG C~95 DEG C, and sample injector furnace temperature soaking time is 55min~65min, and sampling probe temperature is 100 DEG C, transmission line temperature
It is 110 DEG C, nebulizer gas pressure 20psi, sample injection time is 0.02min~0.03min, and pulling out the needle time is 0.2min, pressurization
3.0min。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1538169A (en) * | 2003-04-16 | 2004-10-20 | 中国科学院大连化学物理研究所 | Method of quantitative analysing glutaruldehyde by internal cabel method |
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2017
- 2017-07-28 CN CN201710632146.1A patent/CN109307719A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1538169A (en) * | 2003-04-16 | 2004-10-20 | 中国科学院大连化学物理研究所 | Method of quantitative analysing glutaruldehyde by internal cabel method |
Non-Patent Citations (2)
| Title |
|---|
| INTERNATIONAL ORGANIZATION FOR STANDARDIZATION: "Plastics/rubber – Polymer dispersions and rubber latices (natural and synthetic) – Determination of residual monomers and other organic components by capillary–column gas chromatography – part 2: Headspace method", 《ISO13741-2》 * |
| 陆婷 等: "顶空气相色谱法测定苯丙乳液中残余单体含量", 《中国涂料》 * |
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| CN113082419A (en) * | 2021-04-19 | 2021-07-09 | 四川大学华西医院 | Oxygen inhalation device |
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