CN103575828A - Method for measuring anti-scorching agent CTP of rubber - Google Patents
Method for measuring anti-scorching agent CTP of rubber Download PDFInfo
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- CN103575828A CN103575828A CN201310596245.0A CN201310596245A CN103575828A CN 103575828 A CN103575828 A CN 103575828A CN 201310596245 A CN201310596245 A CN 201310596245A CN 103575828 A CN103575828 A CN 103575828A
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Abstract
The invention provides a method for measuring an anti-scorching agent CTP of rubber. The method comprises the following steps: 1) shearing and extracting a rubber sample to prepare sample extracting liquid; 2) detecting the mass spectrum of the sample extracting liquid by using a gas chromatography-mass spectrum (GC-MS) combined instrument, wherein the condition of detecting the mass spectrum is that EI ion source is adopted, testing is performed to obtain a total ion chromatography, fragment ions are extracted, the mass spectrogram and the phthalimide mass spectrogram are compared, if the phthalimide is not detected, the rubber sample does not have the CTP, and if the phthalimide is detected, the rubber sample has the CTP, and then CTP is quantitatively measured. The anti-scorching agent CTP is identified by a GC-MS method; judgment depends on the phthalimide and is not influenced by the complex matrix; sensitivity and accuracy are high; the detection limit is 0.2 mg/kg. An internal standard method is used for quantifying, so the measuring accuracy is improved.
Description
Technical field
The invention belongs to rubber and rubber compounding analysis field, be specifically related to the qualitative analysis of anti-scorching agent CTP in vulcanizate and elastomeric compound, and without the quantitative analysis method of anti-scorching agent CTP in the vulcanizate using and elastomeric compound.
Background technology
The prevulcanization phenomenon that rubber size occurs because being heated in storage and process is called incipient scorch, the ability that incipient scorch can make sizing material lose flowability and reprocess, affect the production technology of various rubbers, the mainly straightforward procedure addressing this problem is at present adapted anti scorching agent.Anti-scorching agent CTP full name N-cyclohexylthiophthalimide, it is a kind of incipient cure inhibitor, there is the function that postpones initial cure time, be applicable to thiazoles, guanidine class, thiurams, the multiple accelerator system such as sulfenamide, anti-scorch the most effective to sulfenamide promoter wherein, be widely used in rubber size, a small amount of interpolation can significantly improve processing safety, contribute to accelerate some process of rubber, (the impact of anti-scorching agent CTP on properties of rubber of conservation and the energy, intelligence is put etc., < < rubber industry > > the 51st volume in 2004: 32-34).And can improve the storage-stable of sizing material, while preventing from depositing, there is natural vulcanization, the consumption of anti-scorching agent CTP generally between 0.1～0.5 mass parts (polymer content 100 mass parts in rubber) in rubber.
In rubber compounding dissects, identify the consumption that whether has used anti-scorching agent CTP and anti-scorching agent CTP, can be research staff and prevent that incipient scorch from providing information, and improve formula, thereby improvement rubber quality, obtain better economic benefit.
The Main Basis that detects anti-scorching agent CTP in rubber by GC-MS method is: while there is sulfenamide or thiazole accelerator in formula, first anti-scorching agent CTP carries out self and decomposes, the free radical decompositing is combined with promoter, thereby delay promoter performance effect, prevent that rubber from occurring to be cross-linked too early, reaction equation is shown in (1):
In formula (1), M represents accelerant MBT, chemical name 2-mercaptobenzothiazole.
From above-mentioned reaction equation, can find out, CTP can decompose in rubber processing process, finally with three kinds of relevant chemical constitution forms, is present in sizing material, and a kind of is former CTP molecule, a phthalimide, also having a kind of is the complex compound with sulphur and promoter formation.Therefore, CTP molecule or phthalimide in rubber sample, detected, just can infer and in sizing material, be added with anti-scorching agent CTP.The mass spectrogram of phthalimide and CTP is shown in Fig. 1.
In at present known rubber, the authentication method of CTP is the method > > of CTP in infrared spectrum evaluation vulcanized rubber for the < < of people's reports such as Li Shujuan, after soon the extract of vulcanized rubber will concentrate, spread upon on bromination sylvite sheet, under infrared lamp, being baked to solvent thoroughly volatilizees, then adopt infrared spectrometer test, whether utilize in extract infrared spectrum containing O=C-Ar-C=O in phthalimide at (1774 ± 5) cm
-1the characteristic absorpting spectrum peak at place, judges in sizing material, whether to be added with CTP anti scorching agent.
The deficiency of the method is: (1) has only stipulated the authentication method of CTP in vulcanized rubber, the discrimination method of CTP in mixing of rubber is not made to regulation.(2) Jin Nengdui functional group identifies, cannot be definitely to the evaluation of chemical substance.Other function additives that contain O=C-Ar-C=O structure if add in vulcanized rubber, also may be mistaken for anti-scorching agent CTP; (3) method sensitivity is poor, and complicated because of extract substrate, the addition of anti scorching agent in rubber compounding few (<1%), therefore (1774 ± 5) cm on extract infrared spectrum
-1the spectrum peak at place extremely a little less than, and be easily subject to Ester absorption spectra peak (1715～1740cm
-1between) interference.
Summary of the invention
For the problem of prior art existence, the object of the invention is to propose the assay method of anti-scorching agent CTP in a kind of rubber.
The technical scheme that realizes the object of the invention is:
An assay method for anti-scorching agent CTP in rubber, comprises step:
1) rubber sample is shredded to extracting extraction, one or more in use ethanol, acetone, toluene, isopropyl alcohol, methyl alcohol, methylene chloride, methenyl choloride are extraction solvent, prepare sample extract;
2) use gas chromatograph-mass spectrometer (GCMS), detect the mass spectrum of described sample extract, wherein, detecting mass spectrographic condition is: EI ion gun, ionization voltage 70eV, 200～300 ℃ of source temperature, sweep limit m/z is 50～650, test obtains the total ion current figure of sample, in sample total ion current figure, extract the fragmention of mass-to-charge ratio m/z=74-78,100-105,145-150, its mass spectrogram and phthalimide mass spectrogram are made comparisons, if phthalimide do not detected in extract, in rubber sample without anti-scorching agent CTP; If phthalimide detected in sample extract, in rubber sample, there is anti-scorching agent CTP.
Wherein, the extraction of described step 1) sample extract is carried out according to standard GB/T3516-2006.
Wherein, described rubber sample is selected from a kind of or its compound in natural rubber (NR), butadiene rubber (BR), butadiene-styrene rubber (SBR), butyl rubber (IIR), halogenated butyl rubber (BIIR, CIIR), ethylene-propylene-diene rubber (EPDM), nitrile rubber (NBR).
Because storage or used vulcanizate can not determine whether phthalimide loss occurs, therefore cannot accurately be inferred the amount of anti-scorching agent CTP by the amount of test gained phthalimide, therefore the content of described quantitative measurement anti-scorching agent CTP is preferably measured without used rubber sample.
In described assay method, if detect in rubber sample, there is anti-scorching agent CTP, carry out step 3) and quantitatively detect: use GC-MS(gas chromatography-mass spectrography), by contrasting with phthalimide standard solution, the content of quantitative measurement anti-scorching agent CTP;
In quantitative measurement, detecting mass spectrographic condition is EI ion gun, ionization voltage 70eV, 200～300 ℃ of source temperature, select to scan under ion monitoring pattern the m/z of monitoring ion and qualitative detection identical, the selection ion flow graph of testing rubber sample and phthalimide standard solution.
Wherein, described sample extract and phthalimide standard solution add internal standard compound matter before using GC-MS(gas chromatography-mass spectrography) quantitative measurement.Internal standard compound matter be chosen as in extract do not contain, not from extract component generation chemical reaction, different with phthalimide retention time and have a material of stable fragment ion peak.Described internal standard compound matter is selected from naphthalene-d8(naphthalene-d8), pyrene-d10(pyrene-d10), anthracene-d10(anthracene-d10), phenanthrene-d10(phenanthrene-d10), benzo [a] pyrene-d12(benzo (a) pyrene-d12), perylene-d12(perylene-d12), a kind of in triphenylbenzene (triphenylbenzene), preferably, described internal standard compound matter is naphthalene-d8.
Wherein, the mass ratio of the phthalimide in described phthalimide standard solution and internal standard compound matter is between 1:3～30:1; In sample extract, the addition of internal standard compound matter should make data measured be covered by typical curve, and rule of thumb, if the sampling amount of sample is 500mg, the optimum addition of internal standard compound matter should be between 0.1～2.0mg.
Wherein, described standard solution is the solution that phthalimide is dissolved in organic solvent, and described organic solvent is selected from one or more in methenyl choloride, methylene chloride, benzene, toluene, phenixin, ethanol, acetone, toluene, isopropyl alcohol, methyl alcohol.
Wherein, described standard solution is the standard solution of the phthalimide of 4-8 kind variable concentrations, and the concentration range of phthalimide is between 1～100mg/L.
Wherein, the chromatographic column filler that described gas chromatography is used is poly dimethyl polysiloxane or dimethyl arlydene silicone copolymers non-substituted or that part replaces.The poly dimethyl polysiloxane that described part replaces, a kind of in 5～50% diphenyl that substituting group is molar ratio, 5～50% phenyl, 5～20% cyanogen propylbenzenes, 5%-dipropyl benzene.The dimethyl arlydene silicone copolymers that described part replaces is 5%-diphenyl 95%-dimethyl arlydene silicone copolymers.
Wherein, GC conditions is: flow rate of carrier gas 1.0mL/min～2.0mL/min, injector temperature: 250 ℃～350 ℃;
The control program of column temperature is: 30～60 ℃ of initial temperature, 5～20 ℃/min rises to 260～360 ℃, keeps 5-30min.The control of described column temperature can be: 30～60 ℃ of initial temperature, 5～20 ℃/min rises to 260～360 ℃, keeps 5-30min.
In assay method of the present invention, mass spectrographic condition and quantitative mass spectrum condition are different qualitatively, and one is that one of full scan (FS) is to select ion scan (SIM).
Beneficial effect of the present invention is:
(1) by GC-MS method, identify that anti-scorching agent CTP in rubber, by accurately finding material phthalimide to judge, is not subject to the impact of complex matrices, sensitivity and accuracy are all very high, detect and are limited to 0.2mg/kg.
(2) no matter be vulcanizate or elastomeric compound, anti-scorching agent CTP is through GC-MS system testing, and all the form with phthalimide occurs, therefore measure the anti-scorching agent CTP in rubber with GC-MS, method is simple, gets twice the result with half the effort.
(3) select not contain in extract, not from extract component generation chemical reaction, different with phthalimide retention time and to have the material of stable fragment ion peak be internal standard compound matter.Improved the degree of accuracy of measuring.
Accompanying drawing explanation
Fig. 1 is the mass spectrogram of phthalimide and CTP.
Fig. 2 is embodiment 1 Mass Spectrometer Method result, and wherein Fig. 2 a is that total ion current figure, Fig. 2 b are that chromatography of ions figure, Fig. 2 c are the mass spectrogram at the material peak at retention time t=14.30min place.
Fig. 3 is embodiment 2 Mass Spectrometer Method results, and wherein Fig. 3 a is that total ion current figure, Fig. 3 b are that chromatography of ions figure, Fig. 3 c are the mass spectrogram at the material peak at retention time t=13.95min place.
Fig. 4 is embodiment 3 Mass Spectrometer Method results, the total ion current figure that wherein Fig. 4 a is sample, Fig. 4 b extracts fragmention m/z=103,147 in sample total ion current figure to obtain extracting chromatography of ions figure, and Fig. 4 c is the material peak at retention time t=14.03min place, is the mass spectrogram of phthalimide.
Fig. 5 is typical curve.
Embodiment
Now with following most preferred embodiment, the present invention is described, but is not used for limiting the scope of the invention.
The GC-MS using in embodiment is Thermo Fisher ITQ1100 gas chromatograph-mass spectrometer system.
Embodiment 1: the analysis of anti-scorching agent CTP in vulcanized rubber is prepared in laboratory
Vulcanized rubber basic recipe is (mass parts): Natural rubber 30, butadiene rubber BR70; Carbon black N37580, process oil 4.0, stearic acid 2.0, zinc paste 2.0, tackifying resin 4.0, antioxidant 4020 1.6, anti-aging agent RD 1.5, sulphur 1.0, vulcanization accelerator NS 2.2, anti-scorching agent CTP 0.3.Rubber sample total amount 198.6, wherein CTP Theoretical Mass percentage composition 1510.6mg/kg.
Preparation technology: with 1.6 liters of Banbury Banbury mixeies (production of FARREL company), by rubber, carbon black and other compound except sulphur, vulcanization accelerator and anti-scorching agent CTP, mix 6 minutes and be warming up to 160 ℃, thereby obtaining masterbatch, and described masterbatch is cooled to below 90 ℃; Then use opening rubber mixing machine to mix vulcanization accelerator, sulphur and anti-scorching agent CTP in masterbatch, at the temperature of 50 ℃, said mixture is carried out to mixing 10min, thereby obtain rubber composition; The composition being obtained by said method moulding on vulcanizing press (160 ℃ of curing temperatures, cure time 30min) is made to vulcanized rubber flat board or thin slice, make vulcanized rubber sample.
Then detect anti-scorching agent CTP.
Sample is cut into about 1mm
3the granule of left and right, gets 573.0mg micelle, and according to GB/T3516-2006 method, acetone-chloroform (volume ratio 32:68) is solvent, prepares sample extract, and extract is concentrated into 20mL, enters GC/MS systematic analysis.
Chromatographic condition is: column's length: 50m; Internal diameter: 0.25mm; Apply phase: 5% diphenyl-, 95% dimethione; Apply phase thickness: 0.20 μ m to 0.35 μ m.The control program of column temperature is: 50 ℃ of initial temperature, 10 ℃/min rises to 310 ℃, keeps 10min.Carrier gas: He; Flow rate of carrier gas: 1mL/min.Chromatogram mass spectrum intermediate conveyor line temperature: 280 ℃.
1.1 qualitative detection, arrange mass spectrometer test condition: EI ion gun, and ionization voltage 70eV, 250 ℃ of source temperature, full scan, surface sweeping scope (m/z) 50～650, test obtains the total ion current figure of sample.In sample total ion current figure, extract fragmention m/z=103,147, the mass spectrogram of abstract mass peak (Fig. 2 c) and phthalimide mass spectrogram (Fig. 1, upper figure) are made comparisons, analysis and identification phthalimide.
Because rubber extract matrix is complicated, proposing has stronger assorted peak in material mass spectrogram, but contrasts by retention time and main fragmention, and still can judge t=14.30min place proposition material is phthalimide, can determine and in rubber sample, contain CTP.
1.2 quantitatively detect,
(1) mark storing solution preparation in: take 37.8mg naphthalene-8(naphthalene-d8) in 50mL volumetric flask, acetone constant volume.
(2) standard model storing solution preparation: take 105.1mg phthalimide in 50mL volumetric flask, methenyl choloride constant volume (because of phthalimide slightly soluble, can suitably heat and accelerate to dissolve).
(3) standard serial solution preparation: get 5 10mL volumetric flasks, with micropipette rifle, pipette in 500 μ L and mark storing solution in interior respectively, then pipette successively standard model storing solution 50 μ L, 100 μ L, 250 μ L, 400 μ L, 500 μ L in 5 volumetric flasks, with after acetone constant volume, enter GC-MS system testing
(4) sample preparation: pipette in the extract of the 500 interior mark storing solutions in μ L naphthalene-8 after concentrated, mix laggard GC-MS system testing.
Mass spectrum condition is set is: EI ion gun, and ionization voltage 70eV, 250 ℃ of source temperature, select ion monitoring (SIM), scan mode: t=3.5min, m/z=136(detects internal standard compound matter naphthalene-d8); T=12.0min, m/z=103,147(detect phthalimide).Test obtains sample and standard series is selected ion flow graph.
(5) calculate:
By sample and standard series, select ion flow graph to obtain peak area Ax, the As of phthalimide and internal standard compound matter, the Area Ratio RA of phthalimide and internal standard compound matter in standard serial solution of take is horizontal ordinate, mass ratio Rm is ordinate drawing standard curve (seeing Fig. 5, table 1).
Obtain Rm=a*RA+b (2)
In formula (2),
A, b-typical curve fitting coefficient;
The mass ratio of Rm-phthalimide and internal standard compound matter;
The Area Ratio of RA---phthalimide and internal standard compound matter, RA=Ax/As.
By the Area Ratio substitution typical curve of phthalimide in sample extract and internal standard compound matter, calculate the mass ratio Rm=1.24mg of phthalimide and internal standard compound matter in sample.According to formula (3), the content that calculates anti-scorching agent CTP in rubber sample is 1428.8mg/kg.With the CTP comparison (1510.6mg/kg) that preparation adds, relative error is 5.4%.
Wt in formula (3)
cTP---be the content (unit: mg/kg) of CTP in sample;
M
s-be the quality of the internal standard compound that adds in sample extract;
M
0-be the quality of sample;
261,147-be respectively the molecular weight of anti-scorching agent CTP and phthalimide.
Table 1: embodiment 1 data result
Embodiment 2: the evaluation of anti-scorching agent CTP in elastomeric compound
Sample is cut into about 1mm
3the granule of left and right, gets 1.569g micelle, and solvent acetone, according to preparing sample extract described in GB/T3516-2006, is all transferred in test tube after extract is concentrated, and is settled to 20mL.The extract preparing is got to 1 μ l with syringe and enter GC-MS system, use system is Thermo Fisher ITQ1100 gas chromatograph-mass spectrometer, and chromatographic column is TR-5MS capillary chromatograph, and 30m * 0.25mm * 0.25 μ m arranges test condition as table 2:
Table 2:GC-MS chromatographic condition
The total ion current figure that obtains sample (is shown in Fig. 3 a).In sample total ion current figure, extract fragmention m/z=103,147 and obtain extracting chromatography of ions figure (seeing Fig. 3 b), the mass spectrogram of abstract mass peak is analyzed successively, and make comparisons with phthalimide standard substance mass spectrogram, the mass spectrogram at material peak that draws retention time t=13.95min place is close with standard spectrogram, because of rubber extract matrix complexity, in mass spectrogram, occurred stronger assorted peak, but main peak is still the feature fragmention (seeing Fig. 3 c) of phthalimide.Therefore infer in this elastomeric compound sample containing anti-scorching agent CTP.
Embodiment 3: the evaluation of anti-scorching agent CTP in vulcanized rubber
Original vulcanized rubber sample is cut into about 1mm
3the granule of left and right, gets 2.452g micelle, and solvent acetone, according to preparing sample extract described in GB/T3516-2006, is all transferred in test tube after extract is concentrated, and is settled to 20mL.The extract preparing is got to 1 μ l with syringe and enters GC-MS system, use system for Thermo FisherITQ1100 gas chromatograph-mass spectrometer, chromatographic column be TR-5MS capillary chromatograph, 30m * 0.25mm * 0.25 μ m, arranges test condition as table 2:
Table 3:GC-MS chromatographic condition:
The total ion current figure that obtains sample (is shown in Fig. 4 a).In sample total ion current figure, extract fragmention m/z=103,147 and obtain extracting chromatography of ions figure (seeing Fig. 4 b), the mass spectrogram of abstract mass peak is analyzed successively, and make comparisons with phthalimide standard substance mass spectrogram, the material peak that draws retention time t=14.03min place is phthalimide (mass spectrogram of this material is shown in Fig. 4 c).Therefore infer in this vulcanizate sample containing anti-scorching agent CTP.
Embodiment 4: the mensuration of anti-scorching agent CTP in the vulcanized rubber that the natural gum of take is parent formula
First the present embodiment sample passes through the test of embodiment 3 methods, determines and wherein contains anti-scorching agent CTP.It is below quantitative measurement.
1.1 interior mark storing solution preparations: take 37.8mg naphthalene-d8 in 50mL volumetric flask, acetone constant volume.
1.2 standard model storing solution preparations: take 105.1mg phthalimide in 50mL volumetric flask, methenyl choloride constant volume (because of phthalimide slightly soluble, can suitably heat and accelerate to dissolve).
1.3 standard serial solution preparations: get 5 10mL volumetric flasks, with micropipette rifle, pipette in 500 μ L and mark storing solution in interior respectively, then pipette successively standard model storing solution 50 μ L, 100 μ L, 250 μ L, 400 μ L, 500 μ L in 5 volumetric flasks, with after acetone constant volume, enter GC-MS system testing
1.4 sample preparations: sample is cut into about 1mm
3the granule of left and right, gets 1952.3mg micelle, solvent acetone, according to preparing sample extract described in GB/T3516-2006, extract is concentrated into 20mL, adds 500 μ L naphthalene-8(naphthalene-d8) in extract after concentrated, mix laggard GC-MS system testing.Test condition is in Table 4:
Table 4:GC-MS chromatographic condition:
Calculate:
By sample and standard series, select ion flow graph to obtain peak area Ax, the As of phthalimide and internal standard compound matter, the Area Ratio RA of phthalimide and internal standard compound matter in standard serial solution of take is horizontal ordinate, and mass ratio Rm is ordinate drawing standard curve (in Table 5).
By the Area Ratio substitution typical curve of phthalimide in sample extract and internal standard compound matter, calculate the mass ratio Rm=1.84 of phthalimide and internal standard compound matter in sample.According to formula (3), the content that calculates anti-scorching agent CTP in rubber sample is 632.5mg/kg(table 5).
Table 5: embodiment 4 data results
Embodiment 5. be take the mensuration of anti-scorching agent CTP in the elastomeric compound that natural gum is parent formula
First the present embodiment sample passes through the test of embodiment 2 methods, determines and wherein contains anti-scorching agent CTP.It is below quantitative measurement.
1.1 interior mark storing solution preparations: take 31.2mg naphthalene-8(naphthalene-d8) in 50mL volumetric flask, acetone constant volume pipettes 1mL and is settled in 10mL volumetric flask from the solution preparing after mixing, and this solution is interior mark storing solution.
1.2 standard model storing solution preparations: take 49.5mg phthalimide in 50mL volumetric flask, methenyl choloride constant volume (because of phthalimide slightly soluble, can suitably heat and accelerate to dissolve).
1.3 standard serial solution liquid preparations: get 5 10mL volumetric flasks, with micropipette rifle, pipette in 500 μ L and mark storing solution in interior respectively, then pipette successively standard model storing solution 100 μ L, 250 μ L, 500 μ L, 750 μ L, 1000 μ L in 5 volumetric flasks, with after acetone constant volume, enter GC-MS system testing.
1.4 sample preparations: sample is cut into about 1mm
3the granule of left and right, gets 498.7mg micelle, solvent acetone, according to preparing sample extract described in GB/T3516-2006, extract is concentrated into 20mL, adds 500 μ L naphthalene-8(naphthalene-d8) in extract after concentrated, mix laggard GC-MS system testing.
Test condition and calculating are with embodiment 4.Test data the results are shown in Table 6.
Table 6: embodiment 5 data results
Above embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various modification and improvement that the common engineering technical personnel in this area make technical scheme of the present invention, all should fall in the definite protection domain of claims of the present invention.
Claims (10)
1. an assay method for anti-scorching agent CTP in rubber, is characterized in that, comprises step:
1) rubber sample is shredded to extracting extraction, with one or more in ethanol, acetone, toluene, isopropyl alcohol, methyl alcohol, methylene chloride, methenyl choloride, prepare sample extract for solvent;
2) use gas chromatograph-mass spectrometer (GCMS), detect the mass spectrum of described sample extract, wherein, detecting mass spectrographic condition is: EI ion gun, ionization voltage 70eV, 200～300 ℃ of source temperature, sweep limit m/z is 50～650, test obtains the total ion current figure of sample, in sample total ion current figure, extract the fragmention of mass-to-charge ratio m/z=74-78,100-105,145-150, the mass spectrogram of extraction of substance and phthalimide mass spectrogram are made comparisons, if phthalimide do not detected in extract, in rubber sample without anti-scorching agent CTP; If phthalimide detected in sample extract, in rubber sample, there is anti-scorching agent CTP.
2. assay method according to claim 1, it is characterized in that, described rubber sample is selected from elastomeric compound or vulcanizate, and the parent of described elastomeric compound or vulcanizate is a kind of or its compound in natural rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, halogenated butyl rubber, ethylene-propylene-diene rubber, nitrile rubber.
3. assay method according to claim 1, it is characterized in that there is anti-scorching agent CTP if detect in rubber sample, carry out step 3) and quantitatively detect: use GC-MS(gas chromatography-mass spectrography), by contrasting with phthalimide standard solution, the content of quantitative measurement anti-scorching agent CTP;
Wherein, detecting mass spectrographic condition is EI ion gun, ionization voltage 70eV, 200～300 ℃ of source temperature, select to scan under ion monitoring pattern the m/z of monitoring ion and qualitative detection identical, the selection ion flow graph of testing rubber sample and phthalimide standard solution.
4. assay method according to claim 3, it is characterized in that, before described sample extract and phthalimide standard solution are used GC-MS(gas chromatography-mass spectrography) quantitative measurement, add internal standard compound matter, described internal standard compound matter is selected from a kind of in naphthalene-d8, pyrene-d10, anthracene-d10, phenanthrene-d10, benzo [a] pyrene-d12, perylene-d12, triphenylbenzene.
5. assay method according to claim 4, is characterized in that, described internal standard compound matter is naphthalene-d8.
6. assay method according to claim 4, is characterized in that, the phthalimide in described phthalimide standard solution and the mass ratio of internal standard compound matter are between 1:3～30:1.
7. assay method according to claim 3, it is characterized in that, described standard solution is the solution that phthalimide is dissolved in organic solvent, and described organic solvent is selected from one or more in methenyl choloride, methylene chloride, benzene, toluene, phenixin, ethanol, acetone, toluene, isopropyl alcohol, methyl alcohol.
8. assay method according to claim 7, is characterized in that, described standard solution is the standard solution of the phthalimide of 4-8 kind variable concentrations, and the concentration range of phthalimide is between 1～100mg/L.
9. according to the arbitrary described assay method of claim 1～8, it is characterized in that, the chromatographic column filler that gas chromatography is used is poly dimethyl polysiloxane or dimethyl arlydene silicone copolymers non-substituted or that part replaces; The poly dimethyl polysiloxane that described part replaces, substituting group is a kind of in 5～50% diphenyl, 5～50% phenyl, 5～20% cyanogen propylbenzenes, 5%-dipropyl benzene; The dimethyl arlydene silicone copolymers that described part replaces is 5%-diphenyl 95%-dimethyl arlydene silicone copolymers.
10. according to the arbitrary described assay method of claim 1～8, it is characterized in that, GC conditions is: flow rate of carrier gas 1.0mL/min～2.0mL/min, injector temperature: 250 ℃～350 ℃;
The control program of column temperature is: 30～60 ℃ of initial temperature, 5～20 ℃/min rises to 260～360 ℃, keeps 5-30min.
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| CN107525874A (en) * | 2017-08-22 | 2017-12-29 | 北京彤程创展科技有限公司 | The assay method of saturation point, wax and oil content in a kind of rubber and rubber chemicals |
| CN108362791A (en) * | 2018-01-30 | 2018-08-03 | 中国农业科学院茶叶研究所 | Phthalimide detection method in a kind of tealeaves |
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| CN107077592B (en) * | 2014-03-28 | 2021-02-19 | 威斯康星校友研究基金会 | High quality accuracy filtering of improved spectrogram matching of high resolution gas chromatography-mass spectrometry data with a unit resolution reference database |
| CN105784893A (en) * | 2014-12-18 | 2016-07-20 | 北京橡胶工业研究设计院 | Discriminating method of natural rubber and isoprene rubber |
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| CN106198828B (en) * | 2016-08-31 | 2018-06-01 | 北京彤程创展科技有限公司 | The identification method of sulfenamide type accelerators in rubber |
| CN107525874A (en) * | 2017-08-22 | 2017-12-29 | 北京彤程创展科技有限公司 | The assay method of saturation point, wax and oil content in a kind of rubber and rubber chemicals |
| CN107525874B (en) * | 2017-08-22 | 2020-04-07 | 北京彤程创展科技有限公司 | Method for measuring content of saturated components, wax and oil in rubber and rubber auxiliary agent |
| CN108362791A (en) * | 2018-01-30 | 2018-08-03 | 中国农业科学院茶叶研究所 | Phthalimide detection method in a kind of tealeaves |
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