CN109839447A - Method for determining residues acrylonitrile, methylbenzene and ethylbenzene in butyronitrile latex - Google Patents
Method for determining residues acrylonitrile, methylbenzene and ethylbenzene in butyronitrile latex Download PDFInfo
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- CN109839447A CN109839447A CN201711211512.2A CN201711211512A CN109839447A CN 109839447 A CN109839447 A CN 109839447A CN 201711211512 A CN201711211512 A CN 201711211512A CN 109839447 A CN109839447 A CN 109839447A
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- ethylbenzene
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- toluene
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 212
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229920000126 latex Polymers 0.000 title claims abstract description 99
- 239000004816 latex Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 77
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 62
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 title abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002904 solvent Substances 0.000 claims abstract description 68
- 239000000126 substance Substances 0.000 claims abstract description 62
- 238000012937 correction Methods 0.000 claims abstract description 47
- 238000010813 internal standard method Methods 0.000 claims abstract description 3
- 239000000523 sample Substances 0.000 claims description 120
- 150000001875 compounds Chemical class 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 53
- 239000011550 stock solution Substances 0.000 claims description 42
- 238000002347 injection Methods 0.000 claims description 31
- 239000007924 injection Substances 0.000 claims description 31
- 238000005259 measurement Methods 0.000 claims description 20
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000003556 assay Methods 0.000 claims description 11
- -1 alkene nitrile Chemical class 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000005070 sampling Methods 0.000 claims description 7
- 239000006199 nebulizer Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000000717 retained effect Effects 0.000 claims 2
- 125000000532 dioxanyl group Chemical group 0.000 abstract 1
- 229920000459 Nitrile rubber Polymers 0.000 description 72
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 45
- 239000000178 monomer Substances 0.000 description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 31
- 239000012535 impurity Substances 0.000 description 25
- 238000004817 gas chromatography Methods 0.000 description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 15
- 229940113088 dimethylacetamide Drugs 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229920006174 synthetic rubber latex Polymers 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 206010019133 Hangover Diseases 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000011115 styrene butadiene Substances 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 210000004080 milk Anatomy 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 229940059939 kayexalate Drugs 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
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- 238000007598 dipping method Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 238000004445 quantitative analysis Methods 0.000 description 1
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- 239000013558 reference substance Substances 0.000 description 1
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- 239000000072 sodium resin Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
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- Sampling And Sample Adjustment (AREA)
Abstract
The invention relates to a method for measuring residues acrylonitrile, methylbenzene and ethylbenzene in butyronitrile latex, which adopts an internal standard method to measure, wherein the internal standard substance is dioxane, and a solvent is water, and the method mainly comprises the following two steps: 1) determining correction factors of volatilized residues acrylonitrile, methylbenzene and ethylbenzene in the butyronitrile latex, and 2) determining the contents of volatilized three types of substances acrylonitrile, methylbenzene and ethylbenzene to be determined in a butyronitrile latex sample to be determined. The measuring method has good repeatability and high accuracy.
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 measuring method of volatile residue acrylonitrile and toluene, ethylbenzene in gas chromatograph quantitative analysis NBR latex.
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..Currently,
The application field of synthetic 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 residue styrene and propylene in ABS, SAN
Nitrile monomer ", Shao Qiurong, " chemical analysis metering ", and the 1st phase of volume 24, page 80~82, in January, 2015.The document uses gas phase
Chromatography-mass spectroscopy direct-injection technique is determined 2 kinds of residual monomer acrylonitrile and styrene in ABS, SAN plastics." acrylic acid
And its gas chromatography of residual monomer measures research in esters polymer ", Liao Liewen, " Speciality Petrochemicals ", the 1st phase,
In July, 2001.The document carries out the residual monomer in acrylic polymer using gas-chromatography direct-injection technique
Measurement." Determination of Remaining Monomer in 791 Resin Powder by Gas Chromatography ", Chen Ping Zhang, " Shenyang chemical industry ", the 6th phase, the 41st~
Page 43,1997.The document is determined the residual monomer in 791 resin-oatmeals using gas-chromatography direct-injection technique.CN
201010614229.6 disclosing a kind of side 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 the residual monomer in acrylonitritrile-styrene resin and rubber modified resin and molded product." gas-chromatography
Method measures residual monomer in ABS resin ", Wen Haibo, " 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 ml headspace bottle
In, 1cm is then added3Water and 2cm3Inner mark solution, ml headspace bottle is sealed after adding dottle pin；Herein, it is added in rubber latex sample
Water be " 6682-2008 water for analytical laboratory use-Specification and test methods of GB/T " specified in level-one water；(5) it is stirred with electromagnetism
Mix device stirring 30min~4h；(6) at 90 DEG C, sample solution is heated into 1h, after making sample vapor liquid equilibrium, is detected in ml headspace bottle
Top tank air；(7) peak area of internal standard compound and the peak area of determinand are measured；(8) it is volatilized by calculating to finally obtain in latex
The residual monomer of property and the content of other organic principles.
" 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 inner mark solution
With the solvent of Standard Stock solutions, the Determination of Styrene in kayexalate resin is determined." static headspace gas
Phase chromatography measures residual monomer content in styrene-acrylic emulsion ", Lu Ting, " Chinese coating ", and the 7th phase of volume 29, page 66~70,
In July, 2014.The document is determined the residual monomer in styrene-acrylic emulsion using GC headspace injection method.Measurement
When, using inner mark method ration, use water as the solvent of inner mark solution, acetone is as Standard Stock solutions solvent, to styrene-acrylic emulsion
In residual monomer be determined.
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.
" rubber latex exam method styrene butadiene is total by American Society Testing and Materials standard ASTM D 4026-1987
The measurement of polymers residue styrene ", the standard is using gas-chromatography direct-injection technique to the residue benzene second in styrene-butadiene latex
Alkene content is measured, and inner mark method ration is used in continuous mode, (needs that non-ionic surfactant is added in water using water
Agent) solvent as inner mark solution and Standard Stock solutions, the internal standard compound used is methyl styrene.
The standard not only has the characteristics that toxicity is low when using water as solvent, but also avoids dimethylformamide and make solvent
When, solvent peak hangover is serious, and when disturbing the appearance or dimethyl acetamide of toluene in standard substance and making solvent, solvent peak is dragged
Tail, the appearance of ethylbenzene, avoids and makees solvent using dimethylformamide or dimethyl acetamide in severe jamming standard substance
When, due to the disadvantage that the hangover of solvent peak causes solvent and rubber latex sample component separating degree reduces, sensitivity is weak；But comparison text
It offers when being measured using gas-chromatography direct-injection technique to the residue styrene in styrene-butadiene latex, draws one with sample introduction needle
Directly rubber latex sample is injected in gas chromatograph after the rubber latex sample of part, the harm of such sample introduction has: the 1. glue in sample introduction needle
Milk sample product meet high temperature in injection port, and sample introduction needle is easily caused to block；2., can will be many non-targeted in rubber latex sample when direct injected
Compound injecting chromatograph, causing the pollution of instrument injection port bushing pipe, (ASTM D 4026-1987 " starts after general sample introduction 20 times
There is ghost peak "), influence the accuracy of subsequent sample analysis result；3. the matrix of rubber latex sample is water, direct injected can will be a large amount of
Water enter chromatographic column, cause chromatographic column column bleed and form peak, and will lead to very strong baseline noise.Meanwhile comparison text
It offers using solvent of the water as inner mark solution and Standard Stock solutions, using methyl styrene as internal standard compound, standard substance is
Styrene, during preparing inner mark solution and Standard Stock solutions, because methyl styrene and styrene are not soluble in water, because
This, which joined nonionic surface active agent in water, increase methyl styrene and benzene by vibrating dispersion
The solubility of ethylene in water.In vibrating dispersion, the time of oscillation and oscillation dynamics can have a direct impact dispersion effect,
Afterwards the correction factor of the styrene evaporated in styrene-butadiene latex sample, toluene and ethylbenzene and its standard of assay are influenced
True property.
Summary of the invention
The object of the present invention is to provide the measurements of residue acrylonitrile and toluene, ethylbenzene volatile in a kind of NBR latex
Method.Present invention is particularly suitable for using volatile residue acrylonitrile and toluene in inner mark method ration measurement NBR latex,
The method of ethylbenzene.
The measuring method of residue acrylonitrile and toluene, ethylbenzene in a kind of NBR latex, using internal mark method determination, internal standard compound
For dioxane, solvent is water, and main includes following two step: 1) the residue acrylonitrile that in NBR latex evaporates and
The correction factor measurement of toluene, ethylbenzene, 2) three kinds of determinand acrylonitrile evaporating in NBR latex sample to be measured, toluene and
The assay of ethylbenzene.
Step 1) the correction factor measurement needs to prepare inner mark solution and Standard Stock solutions, wraps in Standard Stock solutions
Three kinds of standard substance acrylonitrile, toluene and ethylbenzene are included, internal standard compound is dioxane, and solvent is water；According to three kinds of standard substances
Peak area is calculated the correction factor of three kinds of standard substances by formula (1):
In formula: Rf--- the correction factor of standard substance；As--- the peak area of internal standard compound；mv o--- the matter of standard substance
Amount, unit are gram (g)；Av--- the peak area of standard substance；ms o--- the quality of internal standard compound, unit are gram (g).
The assay of three kinds of determinand acrylonitrile of the step 2), toluene and ethylbenzene is mainly according to internal standard compound and three kinds
The peak area of determinand acrylonitrile, toluene and ethylbenzene；Each determinand in NBR latex sample to be measured is calculated by formula (2)
Content:
In formula: Ai--- the peak area of determinand；ms--- the quality of internal standard compound, unit are milligram (mg)；Rf--- by public affairs
The correction factor that formula (1) obtains；As--- the peak area of internal standard compound；md--- the quality of NBR latex sample to be measured, unit thousand
Gram (kg).
The measuring method of volatile residue acrylonitrile and toluene, ethylbenzene in NBR latex of the present invention, mainly
Correction factor including the acrylonitrile, toluene and the ethylbenzene that evaporate in NBR latex measures, and waves in NBR latex sample to be measured
Two steps of assay of three kinds of determinand acrylonitrile, toluene and the ethylbenzene issued.Detailed process is as follows:
(1) correction factor of the acrylonitrile, toluene and the ethylbenzene that evaporate in NBR 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 dioxane, and solvent is water.Standard inventory
Solution includes three kinds of standard substance acrylonitrile, toluene and ethylbenzene: the body of three kinds of standard substance acrylonitrile, toluene and ethylbenzene and solvent
For product than being 1:30~1:60, solvent is water.
The specific continuous mode of correction factor are as follows: by the proportion of 1mL:2mL:15 μ L~1mL:4mL:45 μ L by water, internal standard
Solution is placed in the ml headspace bottle of head-space sampler with Standard Stock solutions and mixes, and seals the ml headspace bottle of head-space sampler, will mix
The top tank air injecting chromatograph of solution；According to the peak area of three kinds of standard substances, three kinds of standard substances are calculated by formula (1)
Correction factor:
In formula:
Rf--- the correction factor of standard substance；
As--- the peak area of internal standard compound；
mv o--- the quality of the ml headspace bottle Plays substance of step (1) head-space sampler, unit are gram (g)；
Av--- the peak area of standard substance；
ms o--- the quality of internal standard compound in the ml headspace bottle of step (1) head-space sampler, unit are gram (g).
(2) assay of the three kinds of determinand acrylonitrile, toluene and ethylbenzene that are evaporated in NBR latex sample to be measured
The NBR 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；70 DEG C~
At 90 DEG C, 0.5h~2.0h is heated, after the sample vapor liquid equilibrium in the ml headspace bottle of head-space sampler, by the top of head-space sampler
Empty bottle gas injecting chromatograph at the middle and upper levels, obtains the peak area of internal standard compound and three kinds of determinand acrylonitrile, toluene and ethylbenzene；According to
Formula (2) calculates the content of each determinand in NBR latex sample to be measured:
In formula:
Ai--- 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 NBR 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 NBR latex.
Quantitative approach of the present invention is internal standard quanitation.
Volatile residue is acrylonitrile, toluene and ethylbenzene in NBR latex of the present invention.
Internal standard compound described in step (1) of the present invention is dioxane, and solvent is water, and wherein the purity of dioxane is point
It analyses 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 acrylonitrile, toluene and ethylbenzene.
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 is using GC headspace injection method to residue acrylonitrile volatile in NBR latex sample and first
Benzene, ethylbenzene are measured, and NBR latex sample is caused to the blocking of sample introduction needle and to instrument when avoiding direct injected in this way
Pollution, eliminate 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 the determination step of the determinand content evaporated in NBR latex sample to be measured in this way, just no longer need to weight
It is new to prepare inner mark solution；The time is both saved in this way, simplifies operating process, and reduces the use of reagent, has saved cost,
The pollution to environment is also reduced simultaneously.
Inner mark solution of the invention is the mixed solution of dioxane and water, and middle inner mark solution is first compared with the existing technology
For the mixed solution of base styrene and water (needing that nonionic surface active agent is added in water), dioxane combines interior with water
Mark solution has the characteristics that toxicity is low, and the pollution effect that the health and environment to user generate is smaller, more environmentally friendly.Together
When, better than methyl styrene and non-ionic surface is added in the dissolubility of dioxane and water complete miscibility, dioxane and water
The water of activating agent, and the mixed solution of dioxane and water is mixed without vibrating.
Standard Stock solutions of the invention are the mixed solution of water and three kinds of standard substance acrylonitrile, toluene and ethylbenzene,
In the measurement of step 1 correction factor, after inner mark solution is mixed with Standard Stock solutions, internal standard compound dioxy in inner mark solution oneself
Acrylonitrile, toluene and ethylbenzene in ring and Standard Stock solutions is all miscible, compared with the existing technology in use non-ionic surface
Activating agent comes for disperse water and internal standard compound and standard substance, and the Standard Stock solutions that dioxane is combined with three kinds of reference substances are not
Only have the characteristics that toxicity is low, and overcomes non-ionic surfactant need to be added in Standard Stock solutions in the prior art
Agent disperses this defect of the solubility of internal standard compound and standard substance in water, eliminates and nonionic surface active agent point is added
Oscillation step when dissipating, while avoiding the dispersion effect of nonionic surface active agent to standard substance correction factor and its containing
Measure fixed influence.
Using GC headspace injection method to three kinds of determinand acrylonitrile, toluene and the second evaporated in NBR latex
When the content of benzene is measured, chooses water as solvent preparation inner mark solution and be added in NBR latex sample to be measured, can make to be measured
The impurity content evaporated in NBR latex sample reduces by 5%~13% compared with the prior art (international standard ISO 13741-2),
10%~25% is reduced compared with the prior art (American Society Testing and Materials standard ASTM D 4026-1987), this result explanation
When being measured using GC headspace injection method to the determinand evaporated in NBR latex, water as solvent is chosen to match
Inner mark solution processed can reduce interfering substance in sample and improve object to be measured analyte detection to qualitative, the quantitative effect of target to be measured
Accuracy.
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 to choose the nitrile rubber milk sample that dimethylformamide is made by solvent using prior art ISO 13741-2
The chromatogram of volatile component in product；
Fig. 2 is to choose the nitrile rubber milk sample that dimethyl acetamide is made by solvent using prior art ISO 13741-2
The chromatogram of volatile component in product；
Fig. 3 is using prior art ASTM D 4026-1987, and it is molten for choosing water (nonionic surface active agent is added)
The chromatogram of volatile component in the NBR latex sample that agent is made；
Fig. 4 for volatile component in the NBR latex sample made using the method for the present invention chromatogram.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Illustrate the present invention by the following examples, however, the present invention is not limited to these examples.
Synthetic rubber latex NBR latex used in the present invention, dioxane used, acrylonitrile, toluene and ethylbenzene are
Commercially available analytical reagents, the present invention used in instrument are as follows: Agilent company, the U.S. production 7890A gas chromatograph and beauty
The Tubomatrix HS40-trap head-space sampler of PE company, state production.
Embodiment 1
(1) correction factor of the acrylonitrile, toluene and the ethylbenzene that evaporate in NBR latex measures
The internal standard compound dioxane for weighing 18.0mg (being accurate to 0.1mg) is added in the volumetric flask of 50mL, is diluted with water
To graduation mark, sealing is used as inner mark solution after shaking up；It takes the water of about 4.0mL to be added in the volumetric flask of 10mL, adds propylene
Three kinds of nitrile, toluene and ethylbenzene standard substances respectively after about 220 μ L (every kind is accurate to 0.1mg), are diluted with water to graduation mark, after shaking up
Sealing is used as Standard Stock solutions.
0.7mL water, 2.0mL inner mark solution are placed in ml headspace bottle with the Standard Stock solutions of 25 μ L and are mixed, head space is sealed
Bottle, 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, is shunted
It is 40 DEG C than for 10:1, column head pressure 12.0psi, originating column temperature, retains 10min, risen to the heating rate of 6 DEG C/min
170 DEG C, do not retain, then rise to 250 DEG C again with the heating rate of 8 DEG C/min, do not retain, detector temperature is 280 DEG C；Head space
The condition of sample injector are as follows: sample injector furnace temperature is 90 DEG C, and sample injector furnace temperature soaking time is 70min, and sampling probe temperature is 100 DEG C,
Transmission line temperature is 110 DEG C, nebulizer gas pressure 20.0psi, sample injection time 0.04min, and pulling out the needle time is 0.2min, pressurization
It is measured under 3.0min, obtains the peak area of internal standard compound and three kinds of standard substances, correction factor is calculated by formula (1):
In formula:
Rf--- the correction factor of standard substance；
As--- the peak area of internal standard compound；
mv o--- the quality of step (1) ml headspace bottle Plays substance, unit are gram (g)；
Av--- the peak area of standard substance；
ms o--- the quality of internal standard compound in step (1) ml headspace bottle, unit are gram (g).
Calculated correction factor is shown in Table 1.
The correction factor of the acrylonitrile, toluene and the ethylbenzene that are evaporated in 1 NBR latex of table
| Determinand | Correction factor |
| Acrylonitrile | 1.6 |
| Toluene | 0.6 |
| Ethylbenzene | 1.0 |
(2) assay of the three kinds of determinand acrylonitrile, toluene and ethylbenzene that are evaporated in NBR latex sample to be measured
The NBR latex sample for weighing 0.8g, is added in ml headspace bottle；Then the water of 1.1mL and the internal standard of 2.0mL is added
After solution, ml headspace bottle is sealed；At 90 DEG C, 70min is heated, after sample to be tested vapor liquid equilibrium, by ml headspace bottle gas at the middle and upper levels
Injecting chromatograph obtains internal standard compound and three kinds of determinand acrylonitrile, toluene and ethylbenzene under conditions of above-mentioned gas chromatograph
Peak area；The content of each determinand in NBR latex sample to be measured is calculated according to formula (2):
In formula:
Ai--- the peak area of determinand；
ms--- the quality of internal standard compound in step (2) ml headspace bottle, unit are milligram (mg)；
Rf--- the correction factor obtained by formula (1)；
As--- the peak area of internal standard compound；
md--- the quality of NBR latex sample to be measured in step (2) ml headspace bottle, unit are kilogram (kg).
The content for calculating the three kinds of determinand acrylonitrile, toluene and the ethylbenzene that evaporate in NBR latex sample to be measured is shown in
Table 2.
The content (unit: mg/kg) of volatile matter in the NBR latex sample to be measured of table 2
| Experiment number | Acrylonitrile | Toluene | Ethylbenzene | Solvent | Impurity |
| 1 | 71.5 | 26.1 | 93.5 | ---- | 223.4 |
| 2 | 65.3 | 22.7 | 85.6 | ---- | 201.8 |
| Average value | 68.4 | 24.4 | 89.6 | ---- | 212.6 |
When the determinand evaporated in measuring NBR latex sample, prior art ISO 13741-2 uses dimethyl
Formamide makees solvent preparation inner mark solution and Standard Stock solutions, the chromatogram made are shown in Fig. 1.In Fig. 1,1 is acrylonitrile,
2 be dimethylformamide (solvent peak), and 3 be toluene, and 4 be ethylbenzene.Wherein, the peak shape of chromatographic peak 2 is poor, hangover is serious, to
The close toluene peak interference of its retention time is larger, and solvent peak in Fig. 1 in addition to determinand and impurity peaks content are higher；It is existing
Technology ISO 13741-2 makees solvent using dimethyl acetamide and prepares inner mark solution and Standard Stock solutions, the chromatography made
Figure is shown in Fig. 2.In Fig. 2,1 is acrylonitrile, and 2 be toluene, and 3 be dimethyl acetamide (solvent peak), and 4 be ethylbenzene.Wherein, chromatographic peak
3 hangovers are serious, larger to the ethylbenzene peak interference close with its retention time, and solvent peak and impurity in Fig. 2 in addition to determinand
Peak content is also higher；Prior art ASTM D 4026-1987 makees solvent preparation using water (nonionic surface active agent is added)
Inner mark solution and Standard Stock solutions, the chromatogram made is shown in Fig. 3, and in Fig. 3,1 is acrylonitrile, and 2 be toluene, and 3 be ethylbenzene.
It can be seen from the figure that its impurity peaks is more, and content is higher；The method of the present invention evaporates in measurement NBR latex sample
Determinand when, inner mark solution and Standard Stock solutions, the chromatogram made are prepared as solvent using water and see Fig. 4.In Fig. 4
In, 1 is acrylonitrile, and 2 be toluene, and 3 be ethylbenzene.In Fig. 4 in addition to not having solvent peak, impurity peaks are also relatively fewer, content is lower.
Embodiment 2
(1) correction factor of the acrylonitrile, toluene and the ethylbenzene that evaporate in NBR latex measures
The internal standard compound dioxane for weighing 21.0mg (being accurate to 0.1mg) is added in the volumetric flask of 50mL, is diluted with water
To graduation mark, sealing is used as inner mark solution after shaking up；It takes the water of about 3.5mL to be added in the volumetric flask of 10mL, adds propylene
Three kinds of nitrile, toluene and ethylbenzene standard substances respectively after about 210 μ L (every kind is accurate to 0.1mg), are diluted with water to graduation mark, after shaking up
Sealing is used as Standard Stock solutions.
0.9mL water, 2.0mL inner mark solution are placed in ml headspace bottle with the Standard Stock solutions of 30 μ L and are mixed, head space is sealed
Bottle, by the top tank air injecting chromatograph of mixed solution；In the condition of gas chromatograph are as follows: injector temperature is 220 DEG C, is shunted
It is 30 DEG C than for 10:1, column head pressure 12.0psi, originating column temperature, retains 10min, risen to the heating rate of 5 DEG C/min
170 DEG C, do not retain, then rise to 250 DEG C again with the heating rate of 10 DEG C/min, do not retain, detector temperature is 240 DEG C；Top
The condition of empty sample injector are as follows: sample injector furnace temperature is 87 DEG C, and sample injector furnace temperature soaking time is 60min, and sampling probe temperature is 100
DEG C, transmission line temperature is 110 DEG C, nebulizer gas pressure 20.0psi, sample injection time 0.02min, and pulling out the needle time is 0.2min, is added
It is measured under pressure 3.0min, obtains the peak area of internal standard compound and three kinds of standard substances, correction factor is calculated by formula (1):
In formula:
Rf--- the correction factor of standard substance；
As--- the peak area of internal standard compound；
mv o--- the quality of step (1) ml headspace bottle Plays substance, unit are gram (g)；
Av--- the peak area of standard substance；
ms o--- the quality of internal standard compound in step (1) ml headspace bottle, unit are gram (g).
Calculated correction factor is shown in Table 3.
The correction factor of the acrylonitrile, toluene and the ethylbenzene that are evaporated in 3 NBR latex of table
| Determinand | Correction factor |
| Acrylonitrile | 1.5 |
| Toluene | 0.6 |
| Ethylbenzene | 0.9 |
(2) assay of the three kinds of determinand acrylonitrile, toluene and ethylbenzene that are evaporated in NBR latex sample to be measured
The NBR latex sample for weighing 0.6g, is added in ml headspace bottle；Then the water of 1.0mL and the internal standard of 1.8mL is added
After solution, ml headspace bottle is sealed；At 87 DEG C, 60min is heated, after sample to be tested vapor liquid equilibrium, by ml headspace bottle gas at the middle and upper levels
Injecting chromatograph obtains internal standard compound and three kinds of determinand acrylonitrile, toluene and ethylbenzene under conditions of above-mentioned gas chromatograph
Peak area；The content of each determinand in NBR latex sample to be measured is calculated according to formula (2):
In formula:
Ai--- the peak area of determinand；
ms--- the quality of internal standard compound in step (2) ml headspace bottle, unit are milligram (mg)；
Rf--- the correction factor obtained by formula (1)；
As--- the peak area of internal standard compound；
md--- the quality of NBR latex sample to be measured in step (2) ml headspace bottle, unit are kilogram (kg).
The content for calculating the three kinds of determinand acrylonitrile, toluene and the ethylbenzene that evaporate in NBR latex sample to be measured is shown in
Table 4.
The content (unit: mg/kg) of volatile matter in the NBR latex sample to be measured of table 4
| Experiment number | Acrylonitrile | Toluene | Ethylbenzene | Solvent | Impurity |
| 1 | 51.8 | 35.1 | 63.2 | ---- | 152.1 |
| 2 | 45.6 | 30.9 | 69.3 | ---- | 160.5 |
| Average value | 48.7 | 33.0 | 66.3 | ---- | 156.3 |
When the determinand evaporated in measuring NBR latex sample, prior art ISO 13741-2 uses dimethyl
Formamide (or dimethyl acetamide) makees solvent and prepares inner mark solution and Standard Stock solutions, prior art ASTM D 4026-
1987, which make solvent using water (nonionic surface active agent is added), prepares inner mark solution and Standard Stock solutions, these three are existing
When the determinand that the chromatogram and the method for the present invention that technology is made evaporate in measuring NBR latex sample, made using water
Inner mark solution is prepared for solvent and Standard Stock solutions, the chromatogram made are similar to Example 1.Overcome the prior art
When dimethylformamide makees solvent in ISO13741-2, solvent peak hangover is serious, disturbs the appearance of toluene in standard substance, or
When dimethyl acetamide makees solvent, solvent peak hangover, the appearance of ethylbenzene in severe jamming standard substance, while avoiding existing
When technology ASTM D 4026-1987 direct injected, many non-targeted compounds in rubber latex sample can be introduced chromatograph.
Embodiment 3
(1) correction factor of the acrylonitrile, toluene and the ethylbenzene that evaporate in NBR latex measures
The internal standard compound dioxane for weighing 25.0mg (being accurate to 0.1mg) is added in the volumetric flask of 50mL, is diluted with water
To graduation mark, sealing is used as inner mark solution after shaking up；Take the water of about 4mL to be added in the volumetric flask of 10mL, add acrylonitrile,
Three kinds of standard substances of toluene and ethylbenzene respectively after about 200 μ L (every kind is accurate to 0.1mg), are diluted with water to graduation mark, shake up rear close
Envelope is used as Standard Stock solutions.
1.0mL water, 1.5mL inner mark solution are placed in ml headspace bottle with the Standard Stock solutions of 25 μ L and are mixed, head space is sealed
Bottle, 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, is shunted
It is 35 DEG C than for 10:1, column head pressure 12.0psi, originating column temperature, retains 10min, risen to the heating rate of 4. DEG C/min
170 DEG C, do not retain, then rise to 250 DEG C again with the heating rate of 8 DEG C/min, do not retain, detector temperature is 260 DEG C；Head space
The condition of sample injector are as follows: sample injector furnace temperature is 85 DEG C, and sample injector furnace temperature soaking time is 65min, and sampling probe temperature is 100 DEG C,
Transmission line temperature is 110 DEG C, nebulizer gas pressure 20.0psi, sample injection time 0.01min, and pulling out the needle time is 0.2min, pressurization
It is measured under 3.0min, obtains the peak area of internal standard compound and three kinds of standard substances, correction factor is calculated by formula (1):
In formula:
Rf--- the correction factor of standard substance；
As--- the peak area of internal standard compound；
mv o--- the quality of step (1) ml headspace bottle Plays substance, unit are gram (g)；
Av--- the peak area of standard substance；
ms o--- the quality of internal standard compound in step (1) ml headspace bottle, unit are gram (g).
Calculated correction factor is shown in Table 5.
The correction factor of the acrylonitrile, toluene and the ethylbenzene that are evaporated in 5 NBR latex of table
| Determinand | Correction factor |
| Acrylonitrile | 1.6 |
| Toluene | 0.5 |
| Ethylbenzene | 1.9 |
(2) assay of the three kinds of determinand acrylonitrile, toluene and ethylbenzene that are evaporated in NBR latex sample to be measured
The NBR latex sample for weighing 0.5g, is added in ml headspace bottle；Then the water of 0.9mL and the internal standard of 1.5mL is added
After solution, ml headspace bottle is sealed；At 85 DEG C, 65min is heated, after sample to be tested vapor liquid equilibrium, by ml headspace bottle gas at the middle and upper levels
Injecting chromatograph obtains internal standard compound and three kinds of determinand acrylonitrile, toluene and ethylbenzene under conditions of above-mentioned gas chromatograph
Peak area；The content of each determinand in NBR latex sample to be measured is calculated according to formula (2):
In formula:
Ai--- the peak area of determinand；
ms--- the quality of internal standard compound in step (2) ml headspace bottle, unit are milligram (mg)；
Rf--- the correction factor obtained by formula (1)；
As--- the peak area of internal standard compound；
md--- the quality of NBR latex sample to be measured in step (2) ml headspace bottle, unit are kilogram (kg).
The content for calculating the three kinds of determinand acrylonitrile, toluene and the ethylbenzene that evaporate in NBR latex sample to be measured is shown in
Table 6.
The content (unit: mg/kg) of volatile matter in the NBR latex sample to be measured of table 6
| Experiment number | Acrylonitrile | Toluene | Ethylbenzene | Solvent | Impurity |
| 1 | 42.6 | 27.8 | 56.2 | ---- | 133.7 |
| 2 | 47.0 | 32.5 | 50.4 | ---- | 121.9 |
| Average value | 44.8 | 30.2 | 53.3 | ---- | 127.8 |
When the determinand evaporated in measuring NBR latex sample, prior art ISO 13741-2 uses dimethyl
Formamide (or dimethyl acetamide) makees solvent and prepares inner mark solution and Standard Stock solutions, prior art ASTM D 4026-
1987, which make solvent using water (nonionic surface active agent is added), prepares inner mark solution and Standard Stock solutions, these three are existing
When the determinand that the chromatogram and the method for the present invention that technology is made evaporate in measuring NBR latex sample, made using water
Inner mark solution is prepared for solvent and Standard Stock solutions, the chromatogram made are similar to Example 1.Overcome the prior art
When dimethylformamide makees solvent in ISO13741-2, solvent peak hangover is serious, disturbs the appearance of toluene in standard substance, or
When dimethyl acetamide makees solvent, solvent peak hangover, the appearance of ethylbenzene in severe jamming standard substance, while avoiding existing
When technology ASTM D 4026-1987 direct injected, many non-targeted compounds in rubber latex sample can be introduced chromatograph.
Comparative example 1~3
According to method as defined in international standard ISO 13741-2, made using dimethylformamide (or dimethyl acetamide)
Solvent prepares the mixed solution of internal standard compound and standard substance, is measured to the content of the impurity evaporated in NBR latex,
Measurement the results are shown in Table 7.
From 1~embodiment of embodiment 3 and 1~comparative example of comparative example 3 as can be seen that for NBR latex, embodiment 1 is measured
The average value of impurity content is 212.6mg/kg, and the average value that embodiment 2 measures impurity content is 156.3mg/kg, embodiment 3
The average value for measuring impurity content is 127.8mg/kg, and the average value that comparative example 1 measures impurity content is 240.1mg/kg, comparison
The average value that example 2 measures impurity content is 171.1mg/kg, and the average value that comparative example 3 measures impurity content is 135.7mg/.It is logical
When comparison more than crossing can be seen that the determinand that the method for the present invention evaporates in measuring NBR latex sample to be measured, use
Water prepares inner mark solution and Standard Stock solutions as solvent, not only overcomes dimethyl formyl in prior art ISO13741-2
Influence of the amine (or dimethyl acetamide) to object, and the impurity content evaporated in NBR latex sample to be measured can be made
5%~13% is reduced compared with the prior art (international standard ISO 13741-2).
The content of the impurity volatilized in NBR latex sample to be measured in 7 comparative example 1-3 of table
Comparative example 4~6
According to method as defined in American Society Testing and Materials standard ASTM D 4026-1987, (added using water as solvent
Enter nonionic surface active agent) prepare internal standard compound and standard substance mixed solution, it is miscellaneous to what is evaporated in NBR latex
The content of matter is measured, and measurement the results are shown in Table 8.
From 1~embodiment of embodiment 3 and 4~comparative example of comparative example 6 as can be seen that for NBR latex, embodiment 1 is measured
The average value of impurity content is 212.6mg/kg, and the average value that embodiment 2 measures impurity content is 156.3mg/kg, embodiment 3
The average value for measuring impurity content is 127.8mg/kg, and the average value that comparative example 4 measures impurity content is 263.5mg/kg, comparison
The average value that example 5 measures impurity content is 186.0mg/kg, and the average value that comparative example 6 measures impurity content is 143.9mg/.It is logical
When comparison more than crossing can be seen that the determinand that the method for the present invention evaporates in measuring NBR latex sample to be measured, use
Water prepares inner mark solution and Standard Stock solutions as solvent, can make the impurity content evaporated in NBR latex sample to be measured
10%~25% is reduced compared with the prior art (ASTM D 4026-1987).
The content of the impurity volatilized in NBR latex sample to be measured in 8 comparative example 4-6 of table
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 the protection scope of the claims in the present invention.
Claims (10)
1. the measuring method of residue acrylonitrile and toluene, ethylbenzene in a kind of NBR latex, which is characterized in that surveyed using internal standard method
Fixed, internal standard compound is dioxane, and solvent is water, including following two step: 1) residue third evaporated in NBR latex
The three kinds of determinand acrylonitrile correction factor measurement of alkene nitrile and toluene, ethylbenzene, 2) being evaporated in NBR latex sample to be measured,
The assay of toluene and ethylbenzene.
2. measuring method according to claim 1, which is characterized in that in step 1) the correction factor measurement needs to prepare
Solution and Standard Stock solutions are marked, include that three kinds of standard substance acrylonitrile, toluene and ethylbenzene, internal standard compound are in Standard Stock solutions
Dioxane, solvent are water, and according to the peak area of three kinds of standard substances, the correction of three kinds of standard substances is calculated by formula (1)
The factor:
In formula: Rf--- the correction factor of standard substance；As--- the peak area of internal standard compound；mv o--- the quality of standard substance, it is single
Position is gram；Av--- the peak area of standard substance；ms o--- the quality of internal standard compound, unit are gram.
3. measuring method according to claim 2, which is characterized in that the step 2) three kinds of determinand acrylonitrile, toluene
Assay with ethylbenzene is the peak area according to internal standard compound and three kinds of determinand acrylonitrile, toluene and ethylbenzene；It is counted by formula (2)
Calculate the content of each determinand in NBR latex sample to be measured:
In formula: Ai--- the peak area of determinand；ms--- the quality of internal standard compound, unit are milligram；Rf--- it is obtained by formula (1)
The correction factor arrived；As--- the peak area of internal standard compound；md--- the quality of NBR 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: configuration is dense
Degree range is 300 μ g/cm3~600 μ g/cm3Inner mark solution, internal standard compound is dioxane, and solvent is water；Standard Stock solutions
Including three kinds of standard substance acrylonitrile, toluene and ethylbenzene: the volume ratio of three kinds of standard substance acrylonitrile, toluene and ethylbenzene and solvent
For 1:30~1:60, solvent is water.
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 and Standard Stock solutions are placed in the top of head-space sampler by the proportion of 1mL:2mL:15 μ L~1mL:4mL:45 μ L
It is mixed in empty bottle, ml headspace bottle is sealed, by the top tank air injecting chromatograph of mixed solution；According to the peak face of three kinds of standard substances
Product, the correction factor of three kinds of standard substances is calculated by formula (1).
6. measuring method according to claim 3, which is characterized in that three kinds of determinand acrylonitrile, toluene and ethylbenzene
Assay process it is as follows: weigh 0.3g~1g NBR latex sample to be measured, be 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, ml headspace bottle is sealed；At 70 DEG C~90 DEG C
Under, 0.5h~2h is heated, after the sample vapor liquid equilibrium in ml headspace bottle, ml headspace bottle gas injecting chromatograph at the middle and upper levels obtains
The peak area of internal standard compound and three kinds of determinand acrylonitrile, toluene and ethylbenzene；It is calculated in NBR latex sample to be measured according to formula (2)
The content of each determinand.
7. according to the described in any item measuring methods of claim 5 or 6, which is characterized in that the chromatographic condition are as follows: sample introduction
Mouth temperature is 150 DEG C~250 DEG C, split ratio 10:1, column head pressure 12psi, and starting column temperature is 30 DEG C~50 DEG C, is retained
10min rises to 170 DEG C with 2 DEG C/min~6 DEG C/min heating rate, does not retain, then again with 8 DEG C/min~11 DEG C/min
Heating rate rise to 250 DEG C, do not retain, detector temperature be 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. according to the described in any item measuring methods of 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, is passed
Defeated line temperature 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,
Pressurize 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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| CN111257270A (en) * | 2020-02-27 | 2020-06-09 | 宁波海关技术中心 | Method for detecting composition content of each monomer unit in regenerated ABS (acrylonitrile butadiene styrene) plastic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111257270A (en) * | 2020-02-27 | 2020-06-09 | 宁波海关技术中心 | Method for detecting composition content of each monomer unit in regenerated ABS (acrylonitrile butadiene styrene) plastic |
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