CN109307727A - Method for measuring residual monomers and other organic components in carboxylated styrene-butadiene latex - Google Patents
Method for measuring residual monomers and other organic components in carboxylated styrene-butadiene latex Download PDFInfo
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- CN109307727A CN109307727A CN201710631433.0A CN201710631433A CN109307727A CN 109307727 A CN109307727 A CN 109307727A CN 201710631433 A CN201710631433 A CN 201710631433A CN 109307727 A CN109307727 A CN 109307727A
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- styrene
- toluene
- ethylbenzene
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- butadiene latex
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- 229920000126 latex Polymers 0.000 title claims abstract description 92
- 239000004816 latex Substances 0.000 title claims abstract description 85
- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 80
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000002174 Styrene-butadiene Substances 0.000 title claims abstract description 78
- 239000011115 styrene butadiene Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000000178 monomer Substances 0.000 title claims abstract description 43
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 254
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 165
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000002904 solvent Substances 0.000 claims abstract description 65
- 239000000126 substance Substances 0.000 claims abstract description 58
- 238000012937 correction Methods 0.000 claims abstract description 45
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 19
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000532 dioxanyl group Chemical group 0.000 claims abstract description 10
- 238000010813 internal standard method Methods 0.000 claims abstract description 3
- 239000000523 sample Substances 0.000 claims description 102
- 150000001875 compounds Chemical class 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 47
- 239000011550 stock solution Substances 0.000 claims description 37
- 238000005259 measurement Methods 0.000 claims description 29
- 238000002347 injection Methods 0.000 claims description 26
- 239000007924 injection Substances 0.000 claims description 26
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 21
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000005070 sampling Methods 0.000 claims description 7
- 230000005540 biological transmission Effects 0.000 claims description 6
- 239000006199 nebulizer Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000003556 assay Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- FDYSSWYQRTVFIS-UHFFFAOYSA-N buta-1,3-diene 3-phenylprop-2-enoic acid Chemical compound C=CC=C.C(=O)(O)C=CC1=CC=CC=C1 FDYSSWYQRTVFIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000006071 cream Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- 229940058172 ethylbenzene Drugs 0.000 description 71
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 66
- 229940113088 dimethylacetamide Drugs 0.000 description 21
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 238000004817 gas chromatography Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 206010019133 Hangover Diseases 0.000 description 13
- 238000005303 weighing Methods 0.000 description 11
- 229920006174 synthetic rubber latex Polymers 0.000 description 10
- 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
- 238000004458 analytical method Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- -1 alkenes compounds Chemical class 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 241000790917 Dioxys <bee> Species 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229920001084 poly(chloroprene) Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 238000012360 testing method Methods 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000003988 headspace gas chromatography Methods 0.000 description 2
- 229940059939 kayexalate Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-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
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 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
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000072 sodium resin Substances 0.000 description 1
- 238000004611 spectroscopical analysis 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
- 238000010998 test method Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a method for measuring residual monomers and other organic components in carboxylic styrene-butadiene latex, which adopts an internal standard method to measure, wherein an internal standard substance is methyl isobutyl ketone, and a solvent is dioxane, and the method mainly comprises the following two steps: 1) measuring correction factors of residual monomer styrene and other organic components toluene and ethylbenzene volatilized from the carboxylic styrene-butadiene latex, and 2) measuring contents of three substances to be measured, namely styrene, toluene and ethylbenzene volatilized from the carboxylic styrene-butadiene latex. 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
Volatile Determination of Styrene and volatile organic principle toluene in gas chromatograph quantitative analysis carboxylic styrene butadiene latex,
The measuring method of ethylbenzene.
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 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
30min~4h will be stirred by mixing device；(6) at 90 DEG C, sample solution is heated into 1h, after making sample vapor liquid equilibrium, detects ml headspace bottle
Gas at the middle and upper levels；(7) peak area of internal standard compound and the peak area of determinand are measured；(8) it is waved by calculating to finally obtain in latex
The residual monomer of hair 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 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 object of the present invention is to provide volatile Determination of Styrene in a kind of carboxylic styrene butadiene latex and volatile
The measuring method of organic principle toluene, ethylbenzene.Present invention is particularly suitable for using in inner mark method ration measurement carboxylic styrene butadiene latex
The method of volatile Determination of Styrene and volatile organic principle toluene, ethylbenzene.
The measuring method of residual monomer and other organic principles, interior using internal mark method determination in a kind of carboxylic styrene butadiene latex
Mark object is methylisobutylketone, and solvent is dioxane, mainly includes following two step: 1) evaporating in carboxylic styrene butadiene latex
Determination of Styrene and other organic principle toluene and ethylbenzene correction factor measurement, 2) carboxylic styrene butadiene latex sample to be measured
In evaporate three kinds of determinand styrene, toluene and ethylbenzene assay.
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 styrene, toluene and ethylbenzene are included, internal standard compound is methylisobutylketone, and solvent is dioxane；It is marked according to three kinds
The peak area of quasi- substance 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 styrene of the step 2), toluene and ethylbenzene is mainly according to internal standard compound and three kinds
The peak area of determinand styrene, toluene and ethylbenzene；It is waited for by calculating each in carboxylic styrene butadiene latex sample to be measured according to formula (2)
Survey the content of object:
In formula: Av--- 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 carboxylic styrene butadiene latex sample to be measured, unit
For kilogram (kg).
Volatile Determination of Styrene and volatile organic principle first in carboxylic styrene butadiene latex of the present invention
The measuring method of benzene, ethylbenzene, it is main including the correction factor of the styrene, toluene and the ethylbenzene that are evaporated in carboxylic styrene butadiene latex
It measures, the assay two of the three kinds of determinand styrene, toluene and the ethylbenzene that are evaporated in carboxylic styrene butadiene latex sample to be measured
A step.Detailed process is as follows:
(1) correction factor of the styrene, toluene and the ethylbenzene that evaporate in carboxylic styrene butadiene 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 three kinds of standard substance styrene, toluene and ethylbenzene: three kinds of standard substance styrene, toluene and ethylbenzene with
The volume ratio of solvent is 1:30~1:60, and 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 three kinds of standard substances, the correction factor of three kinds of standard substances 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 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) content of the three kinds of determinand styrene, toluene and ethylbenzene that are evaporated in carboxylic styrene butadiene latex sample to be measured
Measurement
The carboxylic styrene butadiene latex sample to be measured for weighing 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, obtains internal standard compound and three kinds to be measured
The peak area of object styrene, toluene and ethylbenzene；Each determinand in carboxylic styrene butadiene latex sample to be measured is calculated according to formula (2)
Content:
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 carboxylic styrene butadiene latex sample to be measured, unit thousand in the ml headspace bottle of step (2) head-space sampler
Gram (kg).
Synthetic rubber latex of the present invention is carboxylic styrene butadiene latex.
Quantitative approach of the present invention is internal standard quanitation.
Volatile residual monomer is styrene in carboxylic styrene butadiene latex of the present invention.
Volatile organic principle is toluene, ethylbenzene in carboxylic styrene butadiene 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, 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 residual monomer benzene second volatile in carboxylic styrene butadiene latex sample
Alkene and volatile organic principle toluene, ethylbenzene are measured, and avoid carboxylic styrene butadiene latex sample when direct injected in this way
It is polluted the blocking of sample introduction needle and 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 the determination step of the determinand content evaporated in carboxylic styrene butadiene latex sample to be measured in this way, just it is not necessarily 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 be methylisobutylketone and dioxane mixed solution, compared with the existing technology in
Inner mark solution is the mixing of methylisobutylketone (or dioxane) and dimethylformamide (or dimethyl acetamide)
For solution, the inner mark solution that methylisobutylketone is combined with dioxane has the characteristics that toxicity is low, strong to the body of user
The pollution effect that health and environment generate is smaller, more environmentally friendly.
Standard Stock solutions of the invention are that the mixing of dioxane and three kinds of standard substance styrene, toluene and ethylbenzene is molten
Liquid, it is middle compared with the existing technology that standard is prepared as solvent and standard substance using dimethylformamide (or dimethyl acetamide)
For stock solution, the Standard Stock solutions that dioxane is combined with three kinds of reference substances not only have the characteristics that toxicity is low, but also
When overcoming that dimethylformamide makees solvent in the prior art, solvent peak hangover is serious, disturbs going out for toluene in standard substance
When peak or dimethyl acetamide make solvent, solvent peak hangover, the appearance of ethylbenzene, avoids and adopts in severe jamming standard substance
When making solvent with dimethylformamide or dimethyl acetamide, since the hangover of solvent peak causes solvent and rubber latex sample component point
It is reduced from degree, the disadvantage that sensitivity is weak；Ensure the toluene and ethylbenzene correction factor using the Standard Stock solutions measurement prepared
Accuracy and reliability；Meanwhile improving the precision of our standard measure.
Using GC headspace injection method to three kinds of determinand styrene, the toluene evaporated in carboxylic styrene butadiene latex
When being measured with the content of ethylbenzene, selection dioxane makees solvent preparation inner mark solution and is added to carboxy styrene-butadiene rubber milk sample to be measured
In product, the determinand toluene evaporated in carboxylic styrene butadiene latex sample to be measured, the more existing skill of head space peak area of ethylbenzene can be made
6%~8% and 3%~6% is respectively increased in art, and toluene, ethylbenzene can be improved as solvent using dioxane in this result explanation
Head space detection sensitivity.
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 carboxylic styrene butadiene latex sample schemes, and in figure, 1 is dimethylformamide；
2 be toluene.
Fig. 2 is that dimethyl acetamide and the Chromatographic Comparison of carboxylic styrene butadiene latex sample scheme, and in figure, 3 be dimethyl acetamide；
4 be ethylbenzene.
Fig. 3 is that the Chromatographic Comparison of dioxane and carboxylic styrene butadiene latex sample schemes, and in figure, 5 be dioxane；6 be toluene；
7 be ethylbenzene.
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 carboxylic styrene butadiene latex, dimethylformamide used, dimethylacetamide
Amine, methylisobutylketone and dioxane are commercially available analytical reagents, instrument used in the present invention are as follows: the Shanghai Pu Mei Ying instrument
The 7890A gas chromatograph that the H97-A type magnetic stirrer of instrument Manufacturing Co., Ltd production, Agilent company of the U.S. produce
The Tubomatrix HS40-trap head-space sampler produced with PE company of the U.S..
Embodiment 1
(1) correction factor of the styrene, toluene and the ethylbenzene that evaporate in carboxylic styrene butadiene latex measures
The internal standard compound methylisobutylketone for weighing 25.0mg (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 200 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.
1.0mL 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 30 DEG C than for 10:1, column head pressure 12.0psi, originating column temperature, retains 10min, risen to the heating rate of 2 DEG C/min
170 DEG C, do not retain, then rise to 250 DEG C again with the heating rate of 9 DEG C/min, do not retain, detector temperature is 250 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 55min, 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, 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 styrene, toluene and the ethylbenzene that are evaporated in 1 carboxylic styrene butadiene latex of table
| Determinand | Correction factor |
| Toluene | 0.3 |
| Ethylbenzene | 0.5 |
| Styrene | 1.2 |
(2) content of the three kinds of determinand styrene, toluene and ethylbenzene that are evaporated in carboxylic styrene butadiene latex sample to be measured
Measurement
The carboxylic styrene butadiene latex sample for weighing 0.5g, is added in ml headspace bottle；Then the water and 2.0mL of 1.0mL is added
After inner mark solution, ml headspace bottle is sealed；With magnetic stirrer 2.5h；At 80 DEG C, 1.0h is heated, sample to be tested gas-liquid is flat
After weighing apparatus, by ml headspace bottle gas injecting chromatograph at the middle and upper levels, under conditions of above-mentioned gas chromatograph, obtain internal standard compound and three kinds to
Survey the peak area of object styrene, toluene and ethylbenzene；It is to be measured that each in carboxylic styrene butadiene latex sample to be measured is calculated according to formula (2)
The content of object:
In formula:
Av--- 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 carboxylic styrene butadiene latex sample to be measured in step (2) ml headspace bottle, unit are kilogram (kg).
Calculate containing for three kinds of determinand styrene, toluene and the ethylbenzene evaporated in carboxylic styrene butadiene latex sample to be measured
Amount is shown in Table 2.
The content of the three kinds of determinand styrene, toluene and ethylbenzene that are evaporated in the carboxylic styrene butadiene latex sample to be measured of table 2
When the determinand evaporated in measuring carboxylic styrene butadiene latex sample, the prior art is made using dimethylformamide
Solvent prepares inner mark solution and Standard Stock solutions, the chromatogram made are shown in Fig. 1.In Fig. 1, the expression of chromatographic peak 1 is two
Methylformamide, peak shape is poor, hangover is serious, larger to toluene peak (chromatographic peak 2) interference close with its retention time；It is existing
Having technology to make using dimethyl acetamide, solvent prepares inner mark solution and Standard Stock solutions, the chromatogram made are shown in Fig. 2.?
In Fig. 2, the expression of chromatographic peak 3 is dimethyl acetamide, and hangover is serious, to the ethylbenzene peak (chromatography close with its retention time
Peak 4) interference it is larger.The method of the present invention measure carboxylic styrene butadiene latex sample in evaporate determinand when, using dioxy oneself
Ring prepares inner mark solution as solvent and Standard Stock solutions, the chromatogram made are shown in Fig. 3.In Fig. 3, chromatographic peak 5 is indicated
It is dioxane, the expression of chromatographic peak 6 is toluene, and the expression of chromatographic peak 7 is ethylbenzene.From figure 3, it can be seen that dioxane
Chromatographic peak peak shape it is symmetrical, without trailing phenomenon, and the retention time of dioxane differs larger with the retention time of toluene,
Avoid the dimethylformamide influence quantitative to toluene.
Embodiment 2
(1) correction factor of the styrene, toluene and the ethylbenzene that evaporate in carboxylic styrene butadiene 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, add three kinds of styrene, toluene and ethylbenzene standard substances respectively about 210 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.
0.8mL water, 1.5mL inner mark solution are placed in ml headspace bottle with the Standard Stock solutions of 22 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 50 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 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 95 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 0.01min, 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 3.
The correction factor of the styrene, toluene and the ethylbenzene that are evaporated in 3 carboxylic styrene butadiene latex of table
| Determinand | Correction factor |
| Toluene | 0.2 |
| Ethylbenzene | 0.5 |
| Styrene | 1.1 |
(2) content of the three kinds of determinand styrene, toluene and ethylbenzene that are evaporated in carboxylic styrene butadiene latex sample to be measured
Measurement
The carboxylic styrene butadiene latex sample for weighing 1.0g, is added in ml headspace bottle；Then the water and 2.1mL of 1.0mL is added
After inner mark solution, ml headspace bottle is sealed；With magnetic stirrer 3.0h；At 85 DEG C, 0.5h is heated, sample to be tested gas-liquid is flat
After weighing apparatus, by ml headspace bottle gas injecting chromatograph at the middle and upper levels, under conditions of above-mentioned gas chromatograph, obtain internal standard compound and three kinds to
Survey the peak area of object styrene, toluene and ethylbenzene；It is to be measured that each in carboxylic styrene butadiene latex sample to be measured is calculated according to formula (2)
The content of object:
In formula:
Av--- 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 carboxylic styrene butadiene latex sample to be measured in step (2) ml headspace bottle, unit are kilogram (kg).
Calculate containing for three kinds of determinand styrene, toluene and the ethylbenzene evaporated in carboxylic styrene butadiene latex sample to be measured
Amount is shown in Table 4.
The content of the three kinds of determinand styrene, toluene and ethylbenzene that are evaporated in the carboxylic styrene butadiene latex sample to be measured of table 4
When the determinand evaporated in measuring carboxylic styrene butadiene latex sample, the prior art uses dimethylformamide
(or dimethyl acetamide) makees solvent preparation inner mark solution and Standard Stock solutions, the chromatogram and the method for the present invention made exist
When the determinand evaporated in measurement carboxylic styrene butadiene latex sample, inner mark solution and mark are prepared as solvent using dioxane
Quasi- stock solution, the chromatogram made are similar to Example 1.When overcoming that dimethylformamide makees solvent in the prior art,
Solvent peak hangover is serious, when disturbing the appearance or dimethyl acetamide of toluene in standard substance and making solvent, solvent peak hangover,
The appearance of ethylbenzene in severe jamming standard substance avoids when using dimethylformamide or dimethyl acetamide making solvent,
Due to the disadvantage that the hangover of solvent peak causes solvent and rubber latex sample component separating degree reduces, sensitivity is weak；It ensures to use and match
The toluene of the Standard Stock solutions measurement of system and the accuracy and reliability of ethylbenzene correction factor.
Embodiment 3
(1) correction factor of the styrene, toluene and the ethylbenzene that evaporate in carboxylic styrene butadiene latex measures
The internal standard compound methylisobutylketone for weighing 22.0mg (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.
0.6mL water, 1.0mL inner mark solution are placed in ml headspace bottle with the Standard Stock solutions of 20 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 230 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 4 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 280 DEG C；Top
The condition of empty sample injector are as follows: sample injector furnace temperature is 90 DEG C, and sample injector furnace temperature soaking time is 55min, 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, 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 5.
The correction factor of the styrene, toluene and the ethylbenzene that are evaporated in 5 carboxylic styrene butadiene latex of table
(2) content of the three kinds of determinand styrene, toluene and ethylbenzene that are evaporated in carboxylic styrene butadiene latex sample to be measured
Measurement
The carboxylic styrene butadiene latex sample for weighing 0.3g, is added in ml headspace bottle；Then the water and 1.8mL of 0.8mL is added
After inner mark solution, ml headspace bottle is sealed；With magnetic stirrer 1.0h；At 90 DEG C, 2.0h is heated, sample to be tested gas-liquid is flat
After weighing apparatus, by ml headspace bottle gas injecting chromatograph at the middle and upper levels, under conditions of above-mentioned gas chromatograph, obtain internal standard compound and three kinds to
Survey the peak area of object styrene, toluene and ethylbenzene；It is to be measured that each in carboxylic styrene butadiene latex sample to be measured is calculated according to formula (2)
The content of object:
In formula:
Av--- 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 carboxylic styrene butadiene latex sample to be measured in step (2) ml headspace bottle, unit are kilogram (kg).
Calculate containing for three kinds of determinand styrene, toluene and the ethylbenzene evaporated in carboxylic styrene butadiene latex sample to be measured
Amount is shown in Table 6.
The content of the three kinds of determinand styrene, toluene and ethylbenzene that are evaporated in the carboxylic styrene butadiene latex sample to be measured of table 6
When the determinand evaporated in measuring carboxylic styrene butadiene latex sample, the prior art uses dimethylformamide
(or dimethyl acetamide) makees solvent preparation inner mark solution and Standard Stock solutions, the chromatogram and the method for the present invention made exist
When the determinand evaporated in measurement carboxylic styrene butadiene latex sample, inner mark solution and mark are prepared as solvent using dioxane
Quasi- stock solution, the chromatogram made are similar to Example 1.When overcoming that dimethylformamide makees solvent in the prior art,
Solvent peak hangover is serious, when disturbing the appearance or dimethyl acetamide of toluene in standard substance and making solvent, solvent peak hangover,
The appearance of ethylbenzene in severe jamming standard substance avoids when using dimethylformamide or dimethyl acetamide making solvent,
Due to the disadvantage that the hangover of solvent peak causes solvent and rubber latex sample component separating degree reduces, sensitivity is weak；It ensures to use and match
The toluene of the Standard Stock solutions measurement of system and 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 to the toluene level evaporated in the carboxylic styrene butadiene latex of embodiment 1 and embodiment 2 into
Row measurement, measurement the results are shown in Table 7.
From embodiment 1, embodiment 2 and comparative example 1~2 as can be seen that for carboxylic styrene butadiene latex, embodiment 1 measures first
The average value of benzene peak area is 47678, and the relative standard deviation that embodiment 1 measures toluene is 4.48%, and embodiment 2 measures toluene
The average value of peak area is 48229, and the relative standard deviation that embodiment 2 measures toluene is 3.72%, and comparative example 1 measures toluene peak
The average value of area is 43845, and the relative standard deviation that comparative example 1 measures toluene is 6.30%, and comparative example 2 measures toluene peak face
Long-pending average value is 44352, and the relative standard deviation that comparative example 2 measures toluene is 5.67%.It can be seen that by comparing above
When the determinand that the method for the present invention evaporates in measuring carboxylic styrene butadiene latex sample to be measured, using dioxane as solvent
Inner mark solution and Standard Stock solutions are prepared, the dimethylformamide chromatographic peak hangover influence quantitative to toluene is not only avoided,
Good repeatability has been obtained, and the head space peak area of toluene can be made to improve 6%~8% compared with the prior art, i.e., by the top of toluene
Empty detection sensitivity is improved.
In 7 comparative example 1-2 of table in carboxylic styrene butadiene latex sample to be measured toluene repeated experiment data
Comparative example 3~4
According to method as defined in international standard ISO 13741-2, using dimethyl acetamide make solvent prepare internal standard compound with
The mixed solution of standard substance, respectively to the ethyl-benzene level evaporated in the carboxylic styrene butadiene latex of embodiment 1 and embodiment 2 into
Row measurement, measurement the results are shown in Table 8.
From embodiment 1, embodiment 2 and comparative example 3~4 as can be seen that for carboxylic styrene butadiene latex, embodiment 1 measures second
The average value of benzene peak area is 2582, and the relative standard deviation that embodiment 1 measures ethylbenzene is 3.37%, and embodiment 2 measures ethylbenzene
The average value of peak area is 1691, and the relative standard deviation that embodiment 2 measures ethylbenzene is 2.57%, and comparative example 3 measures ethylbenzene peak
The average value of area is 2420, and the relative standard deviation that comparative example 3 measures ethylbenzene is 5.11%, and comparative example 4 measures ethylbenzene peak face
Long-pending average value is 1589, and the relative standard deviation that comparative example 4 measures ethylbenzene is 3.89%.It can be seen that by comparing above
When the determinand that the method for the present invention evaporates in measuring carboxylic styrene butadiene latex sample to be measured, using dioxane as solvent
Inner mark solution and Standard Stock solutions are prepared, the dimethyl acetamide chromatographic peak hangover influence quantitative to ethylbenzene is not only avoided,
Good repeatability has been obtained, and the head space peak area of ethylbenzene can be made to improve 3%~6% compared with the prior art, i.e., by the top of ethylbenzene
Empty detection sensitivity is improved.
In 8 comparative example 3-4 of table in carboxylic styrene butadiene latex sample to be measured ethylbenzene 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 carboxylic styrene butadiene latex, which is characterized in that use internal standard
Method measurement, internal standard compound is methylisobutylketone, and solvent is dioxane, mainly includes following two step: 1) carboxylic styrene butadiene latex
In the measurement of the correction factor of the Determination of Styrene that evaporates and other organic principle toluene and ethylbenzene, 2) carboxy styrene-butadiene rubber
The assay of the styrene, toluene and the ethylbenzene that are evaporated in cream.
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 three kinds of standard substance styrene, toluene and ethylbenzene, inner mark solution in Standard Stock solutions
Internal standard compound be methylisobutylketone, the solvent of inner mark solution is dioxane, according to the peak area of three kinds of standard substances, by formula
(1) correction factor of three kinds of standard substances is calculated:
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 1, which is characterized in that the step 2) styrene, toluene and ethylbenzene contain
Measurement is the peak area according to internal standard compound and three kinds of determinand styrene, toluene and ethylbenzene surely；Carboxyl to be measured is calculated by formula (2)
The content of each determinand in styrene-butadiene latex sample:
In formula: AvThe peak area of-determinand；msThe quality of-internal standard compound, unit are milligram；Rf- the school obtained by formula (1)
Positive divisor；AsThe peak area of-internal standard compound；mdThe quality of-carboxylic styrene butadiene 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 methylisobutylketone, and solvent is dioxane；Standard
Stock solution includes three kinds of standard substance styrene, toluene and ethylbenzene: three kinds of standard substance styrene, toluene and ethylbenzene and solvent
Volume ratio be 1:30~1:60, solvent is 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,
Ml headspace bottle is sealed, by the top tank air injecting chromatograph of mixed solution；According to the peak area of three kinds of standard substances, by formula (1)
Calculate the correction factor of three kinds of standard substances.
6. measuring method according to claim 3, which is characterized in that three kinds of determinand styrene, toluene and ethylbenzene
Assay process it is as follows: weigh 0.3g~1g carboxylic styrene butadiene latex sample to be measured, be added to the head space of head-space sampler
In bottle；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；It is stirred with electromagnetism
Mix device stirring 0.5h~4h；At 70 DEG C~90 DEG C, heating 0.5h~2h will be pushed up after the sample vapor liquid equilibrium in ml headspace bottle
Empty bottle gas injecting chromatograph at the middle and upper levels, obtains the peak area of internal standard compound and three kinds of determinand styrene, toluene and ethylbenzene；According to
Formula (2) calculates the content of each determinand in carboxylic styrene butadiene latex sample to be measured.
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 (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296936A (en) * | 1999-11-17 | 2001-05-30 | 中国科学院大连化学物理研究所 | Process for preparing 2,5-dimethyl-2,4-hexadiene |
| 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 |
| CN101198256A (en) * | 2005-06-14 | 2008-06-11 | 明治乳业株式会社 | Method for prevention of formation of abnormal flavor in raw milk or pasteurized milk, and pasteurized milk processed by the method |
| CN101649027A (en) * | 2009-08-21 | 2010-02-17 | 潍坊沃尔特化学有限公司 | Continuous production method of acrylonitrile-chlorinated polyethylene-styrene copolymer resin |
| CN102428141A (en) * | 2009-04-10 | 2012-04-25 | 三菱丽阳株式会社 | Additive for thermoplastic resin and method for producing same, thermoplastic resin composition, and molded article |
| CN102830194A (en) * | 2012-07-06 | 2012-12-19 | 复旦大学 | Method for rapidly detecting residual amount of benzene-based pollutants in plastic particles |
| CN102898650A (en) * | 2012-05-11 | 2013-01-30 | 杭州师范大学 | T-chain unit phenyl-containing MTQ silicon resin and preparation method thereof |
| CN104710436A (en) * | 2013-12-13 | 2015-06-17 | 中国中化股份有限公司 | Pyrazolyl pyrilamine compound and use thereof |
| CN106661136A (en) * | 2014-04-09 | 2017-05-10 | 塞拉尼斯销售德国有限公司 | Process for the emulsion polymerization of free-radically polymerizable, ethylenically unsaturated monomers |
| CN106918654A (en) * | 2015-12-28 | 2017-07-04 | 天士力制药集团股份有限公司 | The assay method of macroreticular resin residual solvent in a kind of plus ginseng piece |
-
2017
- 2017-07-28 CN CN201710631433.0A patent/CN109307727A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296936A (en) * | 1999-11-17 | 2001-05-30 | 中国科学院大连化学物理研究所 | Process for preparing 2,5-dimethyl-2,4-hexadiene |
| 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 |
| CN101198256A (en) * | 2005-06-14 | 2008-06-11 | 明治乳业株式会社 | Method for prevention of formation of abnormal flavor in raw milk or pasteurized milk, and pasteurized milk processed by the method |
| CN102428141A (en) * | 2009-04-10 | 2012-04-25 | 三菱丽阳株式会社 | Additive for thermoplastic resin and method for producing same, thermoplastic resin composition, and molded article |
| CN101649027A (en) * | 2009-08-21 | 2010-02-17 | 潍坊沃尔特化学有限公司 | Continuous production method of acrylonitrile-chlorinated polyethylene-styrene copolymer resin |
| CN102898650A (en) * | 2012-05-11 | 2013-01-30 | 杭州师范大学 | T-chain unit phenyl-containing MTQ silicon resin and preparation method thereof |
| CN102830194A (en) * | 2012-07-06 | 2012-12-19 | 复旦大学 | Method for rapidly detecting residual amount of benzene-based pollutants in plastic particles |
| CN104710436A (en) * | 2013-12-13 | 2015-06-17 | 中国中化股份有限公司 | Pyrazolyl pyrilamine compound and use thereof |
| CN106661136A (en) * | 2014-04-09 | 2017-05-10 | 塞拉尼斯销售德国有限公司 | Process for the emulsion polymerization of free-radically polymerizable, ethylenically unsaturated monomers |
| CN106918654A (en) * | 2015-12-28 | 2017-07-04 | 天士力制药集团股份有限公司 | The assay method of macroreticular resin residual solvent in a kind of plus ginseng piece |
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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